WO2012043453A1 - Epoxy resin composition, prepreg and fiber-reinforced compound material - Google Patents
Epoxy resin composition, prepreg and fiber-reinforced compound material Download PDFInfo
- Publication number
- WO2012043453A1 WO2012043453A1 PCT/JP2011/071842 JP2011071842W WO2012043453A1 WO 2012043453 A1 WO2012043453 A1 WO 2012043453A1 JP 2011071842 W JP2011071842 W JP 2011071842W WO 2012043453 A1 WO2012043453 A1 WO 2012043453A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- epoxy resin
- resin composition
- mass
- parts
- fiber
- Prior art date
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 450
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 450
- 239000000203 mixture Substances 0.000 title claims abstract description 121
- 239000000463 material Substances 0.000 title claims abstract description 92
- 150000001875 compounds Chemical class 0.000 title abstract description 4
- 229920005989 resin Polymers 0.000 claims abstract description 137
- 239000011347 resin Substances 0.000 claims abstract description 137
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 claims abstract description 59
- 239000012783 reinforcing fiber Substances 0.000 claims abstract description 47
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 44
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims abstract description 22
- 150000001412 amines Chemical class 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 229930185605 Bisphenol Natural products 0.000 claims abstract description 12
- 238000005191 phase separation Methods 0.000 claims description 74
- 239000003733 fiber-reinforced composite Substances 0.000 claims description 69
- 229920001400 block copolymer Polymers 0.000 claims description 38
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 32
- 239000000126 substance Substances 0.000 claims description 28
- 230000009477 glass transition Effects 0.000 claims description 24
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 14
- 238000013329 compounding Methods 0.000 claims description 13
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 10
- 229920001577 copolymer Polymers 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- 125000003700 epoxy group Chemical group 0.000 claims description 7
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 6
- 239000000178 monomer Substances 0.000 claims description 6
- 229910052796 boron Inorganic materials 0.000 claims description 5
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 claims description 4
- 229920001485 poly(butyl acrylate) polymer Polymers 0.000 claims description 4
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 4
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 125000004189 3,4-dichlorophenyl group Chemical group [H]C1=C([H])C(Cl)=C(Cl)C([H])=C1* 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- 229920001519 homopolymer Polymers 0.000 claims description 2
- 230000000903 blocking effect Effects 0.000 claims 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 238000005470 impregnation Methods 0.000 abstract description 5
- 239000004842 bisphenol F epoxy resin Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 description 79
- 238000001723 curing Methods 0.000 description 67
- 239000000047 product Substances 0.000 description 53
- 239000000835 fiber Substances 0.000 description 39
- 229920000049 Carbon (fiber) Polymers 0.000 description 23
- 239000004917 carbon fiber Substances 0.000 description 23
- 238000000465 moulding Methods 0.000 description 19
- 239000004593 Epoxy Substances 0.000 description 18
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 13
- 238000005259 measurement Methods 0.000 description 13
- 239000002245 particle Substances 0.000 description 13
- 238000012360 testing method Methods 0.000 description 13
- 229920005992 thermoplastic resin Polymers 0.000 description 13
- 238000005452 bending Methods 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 12
- 230000000694 effects Effects 0.000 description 11
- 229920001971 elastomer Polymers 0.000 description 11
- 229920000428 triblock copolymer Polymers 0.000 description 11
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- -1 alicyclic amines Chemical class 0.000 description 10
- 230000005501 phase interface Effects 0.000 description 10
- 239000011159 matrix material Substances 0.000 description 9
- 229920003023 plastic Polymers 0.000 description 9
- 239000004033 plastic Substances 0.000 description 9
- 239000011342 resin composition Substances 0.000 description 9
- 238000001000 micrograph Methods 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 239000005060 rubber Substances 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- XMTQQYYKAHVGBJ-UHFFFAOYSA-N 3-(3,4-DICHLOROPHENYL)-1,1-DIMETHYLUREA Chemical compound CN(C)C(=O)NC1=CC=C(Cl)C(Cl)=C1 XMTQQYYKAHVGBJ-UHFFFAOYSA-N 0.000 description 6
- 239000004952 Polyamide Substances 0.000 description 6
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 6
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 229920000359 diblock copolymer Polymers 0.000 description 6
- 125000000524 functional group Chemical group 0.000 description 6
- 229920002647 polyamide Polymers 0.000 description 6
- 229920001187 thermosetting polymer Polymers 0.000 description 6
- FVCSARBUZVPSQF-UHFFFAOYSA-N 5-(2,4-dioxooxolan-3-yl)-7-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C(C(OC2=O)=O)C2C(C)=CC1C1C(=O)COC1=O FVCSARBUZVPSQF-UHFFFAOYSA-N 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 5
- 235000013877 carbamide Nutrition 0.000 description 5
- 229920003986 novolac Polymers 0.000 description 5
- IGALFTFNPPBUDN-UHFFFAOYSA-N phenyl-[2,3,4,5-tetrakis(oxiran-2-ylmethyl)phenyl]methanediamine Chemical compound C=1C(CC2OC2)=C(CC2OC2)C(CC2OC2)=C(CC2OC2)C=1C(N)(N)C1=CC=CC=C1 IGALFTFNPPBUDN-UHFFFAOYSA-N 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- 229920002554 vinyl polymer Polymers 0.000 description 5
- PULOARGYCVHSDH-UHFFFAOYSA-N 2-amino-3,4,5-tris(oxiran-2-ylmethyl)phenol Chemical compound C1OC1CC1=C(CC2OC2)C(N)=C(O)C=C1CC1CO1 PULOARGYCVHSDH-UHFFFAOYSA-N 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 239000004642 Polyimide Substances 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 4
- 239000004202 carbamide Substances 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 229920001721 polyimide Polymers 0.000 description 4
- 229920002223 polystyrene Polymers 0.000 description 4
- 238000003825 pressing Methods 0.000 description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 4
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- 238000004804 winding Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- 229910015900 BF3 Inorganic materials 0.000 description 3
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000005062 Polybutadiene Substances 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 3
- 239000004809 Teflon Substances 0.000 description 3
- 229920006362 Teflon® Polymers 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
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- 239000000806 elastomer Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000012943 hotmelt Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000009863 impact test Methods 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
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- 125000006850 spacer group Chemical group 0.000 description 3
- 150000003672 ureas Chemical class 0.000 description 3
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical group O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 description 2
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 2
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 2
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 2
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 2
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 2
- CXXSQMDHHYTRKY-UHFFFAOYSA-N 4-amino-2,3,5-tris(oxiran-2-ylmethyl)phenol Chemical compound C1=C(O)C(CC2OC2)=C(CC2OC2)C(N)=C1CC1CO1 CXXSQMDHHYTRKY-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
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- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
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- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 229920006287 phenoxy resin Polymers 0.000 description 1
- 239000013034 phenoxy resin Substances 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 238000013001 point bending Methods 0.000 description 1
- 229920000191 poly(N-vinyl pyrrolidone) Polymers 0.000 description 1
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 238000009751 slip forming Methods 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/32—Epoxy compounds containing three or more epoxy groups
- C08G59/3236—Heterocylic compounds
- C08G59/3245—Heterocylic compounds containing only nitrogen as a heteroatom
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/32—Epoxy compounds containing three or more epoxy groups
- C08G59/38—Epoxy compounds containing three or more epoxy groups together with di-epoxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
- C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
- C08J5/243—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using carbon fibres
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
- C08J5/249—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs characterised by the additives used in the prepolymer mixture
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
Definitions
- the present invention relates to an epoxy resin composition preferably used as a matrix resin of a fiber reinforced composite material suitable for sports applications and general industrial applications, and a prepreg and a fiber reinforced composite material using the epoxy resin composition as a matrix resin.
- Fiber reinforced composite materials using carbon fibers, aramid fibers, etc. as reinforcing fibers make use of their high specific strength and specific modulus to make structural materials such as aircraft and automobiles, sports applications such as tennis rackets, golf shafts and fishing rods Widely used in general industrial applications.
- a method for producing these fiber reinforced composite materials a method is often used in which a prepreg, which is a sheet-like intermediate material in which reinforcing fibers are impregnated with a matrix resin, is laminated and then cured.
- the method using a prepreg has an advantage that a high-performance fiber-reinforced composite material can be easily obtained because the orientation of the reinforcing fibers can be strictly controlled and the degree of freedom in designing the laminated structure is high.
- the matrix resin used for the prepreg a thermosetting resin is mainly used from the viewpoint of heat resistance and productivity, and an epoxy resin is preferably used from the viewpoint of mechanical properties such as adhesion to reinforcing fibers.
- Measures for improving the elastic modulus of the epoxy resin include addition of inorganic fillers such as carbon nanotubes and blending of an amine type epoxy resin having a high elastic modulus.
- Patent Document 1 by adding an amine-type epoxy resin having a high elastic modulus, the elastic modulus of the epoxy resin is improved, and in a fiber-reinforced composite material in which this is applied as a matrix resin, there is a correlation with the fiber direction compressive strength. A significant improvement in strong fiber direction bending strength has been observed. However, in this method, since the toughness of the epoxy resin is lowered, the impact resistance is lowered.
- thermoplastic resin for example, by blending a block copolymer such as a copolymer composed of styrene-butadiene-methyl methacrylate or a block copolymer composed of butadiene-methyl methacrylate.
- a block copolymer such as a copolymer composed of styrene-butadiene-methyl methacrylate or a block copolymer composed of butadiene-methyl methacrylate
- Patent Documents 2 and 3 Methods for greatly improving the toughness of epoxy resins have been proposed.
- these methods have problems such as reduced heat resistance, deteriorated processability due to thickening, and reduced quality such as void generation. Also, this method has an insufficient elastic modulus.
- An object of the present invention is to improve the drawbacks of the prior art, provide a cured resin having both excellent elastic modulus and toughness, and has a low viscosity and excellent impregnation between reinforcing fibers, and Another object is to provide a prepreg and a fiber reinforced composite material using the epoxy resin composition.
- the cured resin means a cured epoxy resin or epoxy resin composition. The same applies hereinafter.
- An epoxy resin composition comprising an epoxy resin [A1], an epoxy resin [B1], an epoxy resin [C1] and a curing agent [D], wherein [A1] is a bisphenol type epoxy resin having a softening point of 90 ° C. or higher, [ B1] is a tri- or higher functional amine type epoxy resin, and [C1] a bisphenol F type epoxy resin having a number average molecular weight of 450 or less, and the epoxy resins [A1] to [C1] are contained in 100 parts by mass of all epoxy resin components.
- the SP value of the cured resin [B2 ′] obtained by reacting and curing the epoxy resin [B2] with the curing agent [D] has epoxy resins [A2] and [C2].
- the softening point of the epoxy resin [A2] is 90 ° C. or higher, and the softening points of the epoxy resins [B2] and [C2] are both 50 ° C.
- a cured resin obtained by curing the epoxy resin composition has a phase separation structure including [A2] rich phase and [B2] rich phase. The period of the phase separation structure is 1 nm to 1 ⁇ m.
- this invention contains the prepreg containing said epoxy resin composition and a reinforced fiber. Moreover, this invention contains the fiber reinforced composite material formed by hardening said prepreg. Moreover, this invention contains the hardened
- a fine phase separation structure of an epoxy resin is formed at the time of curing, a high elastic modulus and high toughness resin cured product is obtained, and the epoxy resin composition has a low viscosity and excellent impregnation between reinforcing fibers.
- cured material of the epoxy resin composition of this invention as matrix resin has the outstanding static strength characteristic and impact resistance.
- the epoxy resin composition provides an epoxy resin [A] that gives the resin cured product high toughness, and an epoxy resin that gives the resin cured product a high elastic modulus [ B], an epoxy resin [C] that functions as a compatibilizing agent for epoxy resins [A] and [B], and a curing agent [D], and a resin curing obtained by curing the epoxy resin composition
- a cured product having a high elastic modulus and high toughness can be obtained by forming a fine phase separation structure including an epoxy resin [A] rich phase and an epoxy resin [B] rich phase.
- the spinodal decomposition occurs in the curing process, and the epoxy resin [A] rich phase and the epoxy resin [ B] It is preferable to form a phase separation structure with the rich phase. Further, the phase separation structure period is more preferably 1 nm to 5 ⁇ m, and a more preferable phase separation structure period is 1 nm to 1 ⁇ m.
- the epoxy resin [C] functions as a compatibilizing agent for the epoxy resins [A] and [B].
- the structural period When the structural period is less than 1 nm, the cavitation effect cannot be exhibited, and not only the toughness is insufficient but also the elastic modulus tends to be insufficient.
- the structural period exceeds 5 ⁇ m, the structural period is large, so the crack does not progress to the island phase, but only in the sea phase.
- the toughness may be insufficient. That is, the cured product of the epoxy resin composition contains an epoxy resin [A] rich phase and an epoxy resin [B] rich phase, and has a fine phase separation structure, so that the elastic modulus and toughness of the resin cured product can be improved. It is possible to achieve both.
- the phase separation structure means a structure in which two or more phases including an epoxy resin [A] rich phase and an epoxy resin [B] rich phase are separated.
- the epoxy resin [A] rich phase and the epoxy resin [B] rich phase refer to phases mainly composed of the epoxy resin [A] and the epoxy resin [B], respectively.
- a main component means the component contained by the highest content rate in the said phase here.
- the phase separation structure may be a phase separation structure of three or more phases further including a phase mainly composed of components other than the epoxy resin [A] and the epoxy resin [B].
- the state of being uniformly mixed at the molecular level is called a compatible state.
- phase separation structure of the cured resin product can be observed with a scanning electron microscope or a transmission electron microscope. You may dye
- the structural period of phase separation is defined as follows.
- the phase separation structure includes a two-phase continuous structure and a sea-island structure.
- draw three straight lines of a predetermined length on the micrograph draw three straight lines of a predetermined length on the micrograph, extract the intersection of the straight line and the phase interface, measure the distance between the adjacent intersections, These number average values are used as the structure period.
- the predetermined length is set as follows based on a micrograph.
- a sample photograph was taken at a magnification of 20,000 times, and a length of 20 mm drawn on the photograph (1 ⁇ m on the sample) Is a predetermined length of a straight line.
- the phase separation structure period is expected to be on the order of 0.1 ⁇ m (0.1 ⁇ m or more and less than 1 ⁇ m)
- a photograph is taken at a magnification of 2,000 times and a length of 20 mm on the photograph (10 ⁇ m on the sample) (Length) is a predetermined length of a straight line.
- phase separation structure period When the phase separation structure period is expected to be on the order of 1 ⁇ m (1 ⁇ m or more and less than 10 ⁇ m), a photograph is taken at a magnification of 200 times, and a length of 20 mm on the photograph (a length of 100 ⁇ m on the sample) is defined as a predetermined straight line length. To do. If the measured phase separation structure period is out of the expected order, the measurement is performed again at a magnification corresponding to the corresponding order.
- the phase separation structure is a sea-island structure
- three predetermined regions on the micrograph are selected at random, the island phase size in the region is measured, and the number average value of these is the structure period.
- the size of the island phase refers to the length of the shortest distance line drawn from the phase interface to one phase interface through the island phase. Even when the island phase is an ellipse, an indeterminate shape, or a circle or ellipse of two or more layers, the shortest distance passing through the island phase from the phase interface to one phase interface is defined as the island phase size.
- the predetermined area is set as follows based on a micrograph.
- phase separation structure period When the phase separation structure period is expected to be on the order of 0.01 ⁇ m (0.01 ⁇ m or more and less than 0.1 ⁇ m), a photograph of the sample was taken at a magnification of 20,000 times, and an area of 4 mm square on the photograph (0 on the sample) .2 ⁇ m square area) is defined as a predetermined area. Similarly, when the phase separation structure period is expected to be on the order of 0.1 ⁇ m (0.1 ⁇ m or more and less than 1 ⁇ m), a photograph is taken at a magnification of 2,000 times, and an area of 4 mm square on the photograph (2 ⁇ m square on the sample) Is defined as a predetermined area.
- phase separation structure period When the phase separation structure period is expected to be on the order of 1 ⁇ m (1 ⁇ m or more and less than 10 ⁇ m), a photograph is taken at a magnification of 200 times, and an area of 4 mm square on the photograph (an area of 20 ⁇ m square on the sample) is defined as a predetermined area. If the measured phase separation structure period is out of the expected order, the measurement is performed again at a magnification corresponding to the corresponding order.
- a first aspect of the epoxy resin composition of the present invention is an epoxy resin composition comprising an epoxy resin [A1], an epoxy resin [B1], an epoxy resin [C1], and a curing agent [D], wherein [A1] Is a bisphenol type epoxy resin having a softening point of 90 ° C.
- [B1] is a trifunctional or higher amine type epoxy resin
- [C1] is a bisphenol F type epoxy resin having a number average molecular weight of 450 or less
- the epoxy resin [A1 ] To [C1] satisfy the compounding ratio of [A1] 20 to 50 parts by mass, [B1] 30 to 50 parts by mass and [C1] 10 to 40 parts by mass with respect to 100 parts by mass of all epoxy resin components. It is a resin composition.
- the epoxy resin [A1] needs to contain 20 to 50 parts by mass of 100 parts by mass of the total epoxy resin of bisphenol type epoxy resin having a softening point of 90 ° C. or higher. Preferably, 30 to 50 parts by mass of the epoxy resin [A1] is included in 100 parts by mass of the total epoxy resin.
- the softening point of the epoxy resin [A1] is less than 90 ° C., the toughness of the cured resin is insufficient.
- content of epoxy resin [A1] is less than 20 mass parts, the toughness of resin cured material is insufficient.
- the content of the epoxy resin [A1] exceeds 50 parts by mass, not only the elastic modulus and heat resistance of the resin cured product are insufficient, but also the viscosity of the epoxy resin composition becomes too high. If the viscosity of the epoxy resin composition becomes too high, the epoxy resin composition cannot be sufficiently impregnated between the reinforcing fibers when the prepreg is produced. For this reason, voids are generated in the obtained fiber reinforced composite material, and the strength of the fiber reinforced composite material is lowered.
- the epoxy resin [A1] is selected from bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, bisphenol S type epoxy resin, and halogen-substituted products, alkyl-substituted products, hydrogenated products, etc.
- An epoxy resin can be preferably used.
- Examples of such commercially available epoxy resin [A1] include “jER (registered trademark)” 1004AF, 1007, 1009P, 1010P, 4005P, 4007P, 4009P, and 4010P (above, manufactured by Mitsubishi Chemical Corporation).
- bisphenol A type epoxy resin or bisphenol F type epoxy resin is preferable, and bisphenol F type epoxy resin is more preferable because of a good balance of heat resistance, elastic modulus, and toughness.
- the epoxy resin [B1] needs to contain 30 to 50 parts by mass of trifunctional or higher amine type epoxy resin out of 100 parts by mass of the total epoxy resin.
- the content of the epoxy resin [B1] is less than 30 parts by mass, the elastic modulus of the resin cured product is insufficient.
- content of epoxy resin [B1] exceeds 50 mass parts, the plastic deformation capability and toughness of resin hardened
- the tri-functional amine-type epoxy resins are preferable because they give the cured resin a good balance between elastic modulus and toughness.
- aminophenol type epoxy resins are more preferable because the toughness of the cured resin is relatively high.
- epoxy resin [B1] examples include amine type epoxy resins such as tetraglycidyldiaminodiphenylmethane, tetraglycidyldiaminodiphenylsulfone, tetraglycidyldiaminodiphenylether, triglycidylaminophenol, triglycidylaminocresol, tetraglycidylxylylenediamine, and triglycidyl.
- Epoxy resins having an isocyanurate skeleton and epoxy resins selected from halogen-substituted products, alkyl-substituted products, hydrogenated products and the like are preferably used.
- tetraglycidyldiaminodiphenylmethane examples include “Sumiepoxy (registered trademark)” ELM434 (manufactured by Sumitomo Chemical Co., Ltd.), YH434L (manufactured by Nippon Steel Chemical Co., Ltd.), and “jER (registered trademark)” 604 (Mitsubishi Chemical Corporation). ), “Araldide (registered trademark)” MY720, MY721 (manufactured by Huntsman Advanced Materials), and the like.
- tetraglycidyl diaminodiphenyl ether 3,3′-TGDDE (manufactured by Toray Fine Chemical Co., Ltd.) or the like can be used.
- triglycidylaminophenol or triglycidylaminocresol “Araldide (registered trademark)” MY0500, MY0510, MY0600 (manufactured by Huntsman Advanced Materials), “jER (registered trademark)” 630 (Mitsubishi Chemical Corporation) ))
- Aldide registered trademark
- Tetraglycidylxylylenediamine and its hydrogenated product may be “TETRAD (registered trademark)”-X, “TETRAD (registered trademark)”-C (above, manufactured by Mitsubishi Gas Chemical Co., Ltd.), etc. .
- TG3DAS tetraglycidyl diaminodiphenyl sulfone
- the epoxy resin [C1] gives a high elastic modulus, it is necessary to use bisphenol F type epoxy resin having a number average molecular weight of 450 or less of 10 to 40 parts by mass out of 100 parts by mass of the total epoxy resin.
- the epoxy resin [C1] is contained in 20 to 40 parts by mass out of 100 parts by mass of the total epoxy resin.
- the compounding quantity of epoxy resin [C1] exceeds 40 mass parts, the toughness of the resin cured material obtained tends to be insufficient.
- the compounding quantity of epoxy resin [C1] is less than 10 mass parts, the viscosity of an epoxy resin composition may become high.
- the viscosity of the epoxy resin composition obtained can be made low by making the number average molecular weight of epoxy resin [C1] 450 or less. Therefore, in the prepreg manufacturing process, the epoxy resin composition is easily impregnated between the reinforcing fibers, so that the fiber content of the obtained prepreg can be improved.
- the number average molecular weight of the epoxy resin [C1] is larger than 450, the viscosity of the epoxy resin composition tends to be high, so that the epoxy resin composition is difficult to impregnate between the reinforcing fibers in the prepreg manufacturing process. It tends to be difficult to improve the fiber content.
- the effect as a compatibilizing agent becomes large because the number average molecular weight of epoxy resin [C1] is 450 or less, it is easy to form a fine phase-separation structure.
- the number average molecular weight of the bisphenol F type epoxy resin [C1] is larger than 450, the component [C1] is easily compatible with any one of the phases, so that the effect as a compatibilizer tends to be small. As a result, the phase separation structure period of the cured resin tends to increase.
- the number average molecular weight as used in the field of this invention is the value calculated
- the curing agent [D] is not particularly limited as long as it cures an epoxy resin, and amines such as aromatic amines and alicyclic amines, acid anhydrides, polyaminoamides, organic acid hydrazides, isocyanates And the like.
- An amine curing agent is preferable because the cured resin obtained has excellent mechanical properties and heat resistance.
- the amine curing agent diaminodiphenyl sulfone and diaminodiphenylmethane which are aromatic amines, dicyandiamide or a derivative thereof which is an aliphatic amine, hydrazide compounds, and the like are used.
- Examples of such commercially available dicyandiamide include DICY-7 and DICY-15 (manufactured by Mitsubishi Chemical Corporation).
- the dicyandiamide derivative is obtained by bonding various compounds to dicyandiamide, and includes a reaction product with an epoxy resin, a reaction product with a vinyl compound or an acrylic compound.
- dicyandiamide or a derivative thereof as a curing agent [D] is blended into an epoxy resin composition from the viewpoint of storage stability at room temperature and viscosity stability during prepreg formation.
- the average particle size is preferably 10 ⁇ m or less, more preferably 7 ⁇ m or less.
- dicyandiamide or a derivative thereof having a particle size of more than 10 ⁇ m does not enter the reinforcing fiber bundle and remains on the surface of the fiber bundle. There is a case.
- the total amount of the curing agent [D] preferably includes an amount such that the active hydrogen groups are in the range of 0.6 to 1.0 equivalent with respect to the epoxy groups of all the epoxy resin components contained in the epoxy resin composition. More preferably, it is in the range of 0.7 to 0.9 equivalent.
- the active hydrogen group is less than 0.6 equivalent, the reaction rate, heat resistance and elastic modulus of the resin cured product are insufficient, and the glass transition temperature and strength of the obtained fiber reinforced composite material may be insufficient.
- the active hydrogen group exceeds 1.0 equivalent, the reaction rate, glass transition temperature and elastic modulus of the cured resin are sufficient, but the plastic deformation ability is insufficient, so that the resulting fiber-reinforced composite material has a resistance to resistance. Impact may be insufficient.
- Each curing agent may be used in combination with a curing accelerator or other epoxy resin curing agent.
- the curing accelerator to be combined include ureas, imidazoles, and Lewis acid catalysts.
- urea compound examples include N, N-dimethyl-N ′-(3,4-dichlorophenyl) urea, toluene bis (dimethylurea), 4,4′-methylenebis (phenyldimethylurea), and 3-phenyl-1 , 1-dimethylurea and the like can be used.
- examples of commercially available urea compounds include DCMU99 (manufactured by Hodogaya Chemical Co., Ltd.), “Omicure (registered trademark)” 24, 52, and 94 (manufactured by CVC Specialty Chemicals, Inc.).
- Lewis acid catalysts include boron trifluoride / piperidine complex, boron trifluoride / monoethylamine complex, boron trifluoride / triethanolamine complex, boron trichloride / octylamine complex, etc. Is mentioned.
- urea compounds are preferably used from the balance between storage stability and catalytic ability.
- the amount of the urea compound is preferably 1 to 3 parts by mass with respect to 100 parts by mass of all the epoxy resin components contained in the epoxy resin composition.
- the compounding amount of the urea compound is less than 1 part by mass, the reaction does not proceed sufficiently, and the elastic modulus and heat resistance of the cured resin product tend to decrease.
- the compounding quantity of a urea compound exceeds 3 mass parts, since the self-polymerization reaction of an epoxy resin inhibits reaction with an epoxy resin and a hardening
- the second embodiment of the epoxy resin composition of the present invention comprises an epoxy resin [A2], an epoxy resin [B2], an epoxy resin [C2] and a curing agent [D], and the following conditions (1) to ( An epoxy resin composition satisfying 4): (1) The SP value of the cured resin [B2 ′] obtained by reacting the epoxy resin [B2] with the curing agent [D] and curing the epoxy resin [A2] and [C2] is the curing agent [D]. Greater than the SP value of any of the cured resin products [A2 ′] and [C2 ′] obtained by reacting with and curing the resin; (2) The softening point of the epoxy resin [A2] is 90 ° C.
- An epoxy resin composition comprising (3,4-dichlorophenyl) -1,1-dimethylurea (hereinafter referred to as DCMU) was heated from room temperature to 130 ° C. at a rate of 2.5 ° C./min and then at 130 ° C. for 90 minutes.
- the elastic modulus of the cured resin obtained by reacting is 3.5 GPa or more; and (4) The cured resin obtained by reacting and curing the epoxy resins [A2] to [C2] with the curing agent [D]. However, it has a phase separation structure including [A2] rich phase and [B2] rich phase, and the phase separation structure period is 1 nm to 1 ⁇ m.
- the cured resin products [A2 ′], [B2 ′], and [C2 ′ obtained by reacting the epoxy resins [A2], [B2], and [C2] with the curing agent [D], respectively. ] Must satisfy the following condition. (1) (SP value of [B2 ′]) ⁇ (SP value of [A2 ′]) + 1.2 (2) (SP value of [B2 ′]) ⁇ (SP value of [C2 ′]) + 1.2
- the SP value is a generally known solubility parameter, and is an index of solubility and compatibility.
- the SP value defined in the present invention is Polym. Eng. Sci.
- the softening point of the epoxy resin [A2] is 90 ° C. or higher and the softening points of the epoxy resins [B2] and [C2] are 50 ° C. or lower.
- the epoxy resins [A2] to [C2] satisfy these requirements, it is possible to prevent [A2] from being compatible with [B2] and obtaining a uniform structure in the obtained resin cured product. Both rate and toughness are improved.
- the epoxy resin [C2] an amount of dicyandiamide in which the active hydrogen group is 0.9 equivalent to the epoxy group of the epoxy resin [C2], and 100 parts by mass of the epoxy resin [C2]
- the epoxy resin composition comprising 2 parts by mass of DCMU is heated from room temperature to 130 ° C. at 2.5 ° C./min and reacted at 130 ° C. for 90 minutes, and the elastic modulus of the cured resin obtained is 3. It needs to be 5 GPa or more. When the elastic modulus of the cured resin is less than 3.5 GPa, the cured resin obtained from the epoxy resin composition of the present invention cannot obtain a good elastic modulus.
- the epoxy resin [C2] acts as a compatibilizing agent and is a component that dissolves in both the [A2] rich phase and the [B2] rich phase, and thus the resin obtained by the high elastic modulus of the epoxy resin [C2]
- the elastic modulus of the cured product is increased.
- the phase separation structure is a sea-island structure
- it is important that the sea phase covering the island phase has a high elastic modulus. Therefore, when the epoxy resin [C2] is dissolved in the sea phase, the sea phase has a high elastic modulus.
- the active hydrogen group means a functional group that can react with an epoxy group. Examples of the active hydrogen group include an amino group and a hydroxyl group.
- the cured resin obtained by curing the epoxy resin composition has a phase separation structure including an epoxy resin [A2] rich phase and an epoxy resin [B2] rich phase, and the phase separation structure The period must be 1 nm to 1 ⁇ m.
- both the elastic modulus and toughness of the cured resin can be achieved.
- the structural period is less than 1 nm, the cavitation effect cannot be exhibited, and not only the toughness is insufficient but also the elastic modulus is insufficient.
- the structural period exceeds 1 ⁇ m, the structural period is large, so the crack does not progress to the island phase, but only in the sea phase, so the cavitation effect cannot be expressed and the toughness is insufficient. It becomes.
- epoxy resin [A2] an epoxy selected from bisphenol type epoxy resins having a softening point of 90 ° C. or higher, isocyanate-modified epoxy resins, anthracene type epoxy resins and halogen-substituted products, alkyl-substituted products, hydrogenated products, etc.
- a resin can be preferably used.
- the epoxy resin [A2] is preferably contained in an amount of 20 to 50 parts by mass of 100 parts by mass of the total epoxy resin, and more preferably 30 to 50 parts by mass of 100 parts by mass of the total epoxy resin.
- the obtained resin cured product tends to be difficult to form a phase separation structure, and the toughness tends to decrease.
- the content exceeds 50 parts by mass, not only the elastic modulus and heat resistance of the cured resin product tends to be lowered, but also the viscosity of the epoxy resin composition tends to be too high. If the viscosity of the epoxy resin composition becomes too high, the epoxy resin composition may not be sufficiently impregnated between the reinforcing fibers when the prepreg is produced. For this reason, voids are generated in the obtained fiber-reinforced composite material, and the strength of the fiber-reinforced composite material may be reduced.
- an amine-type epoxy resin such as tetraglycidyldiaminodiphenylmethane, tetraglycidyldiaminodiphenylether, triglycidylaminophenol, triglycidylaminocresol, tetraglycidylxylylenediamine having a softening point of 50 ° C. or less, Epoxy resins having a triglycidyl isocyanurate skeleton and epoxy resins selected from halogen-substituted products, alkyl-substituted products, hydrogenated products, and the like can be used.
- tetraglycidyldiaminodiphenylmethane examples include “Sumiepoxy (registered trademark)” ELM434 (manufactured by Sumitomo Chemical Co., Ltd.), YH434L (manufactured by Nippon Steel Chemical Co., Ltd.), and “jER (registered trademark)” 604 (Mitsubishi Chemical Corporation). ), “Araldide (registered trademark)” MY720, MY721 (manufactured by Huntsman Advanced Materials), etc. can be used.
- tetraglycidyl diaminodiphenyl ether 3,3′-TGDDE (manufactured by Toray Fine Chemical Co., Ltd.) or the like can be used.
- triglycidylaminophenol or triglycidylaminocresol “Araldide (registered trademark)” MY0500, MY0510, MY0600 (manufactured by Huntsman Advanced Materials), “jER (registered trademark)” 630 (manufactured by Mitsubishi Chemical Corporation) ) Etc. can be used.
- TETRAD tetraglycidylxylylenediamine and hydrogenated products thereof
- TETRAD registered trademark
- TETRAD registered trademark
- C manufactured by Mitsubishi Gas Chemical Co., Inc.
- TEPIC registered trademark
- the epoxy resin [B2] is preferably a tri- or higher functional amine type epoxy resin.
- the epoxy resin [B2] is preferably contained in 30 to 50 parts by mass out of 100 parts by mass of the total epoxy resin.
- the tri- or higher functional amine-type epoxy resins the tri-functional amine-type epoxy resins are preferable because they give the cured resin a good balance between elastic modulus and toughness.
- aminophenol type epoxy resins have relatively high toughness and are more preferable.
- epoxy resin [C2] a bisphenol F type epoxy resin, a bisphenol AD type epoxy resin, a bisphenol S type epoxy resin, a phenol novolak type epoxy resin having a softening point of 50 ° C. or less, halogen substitution products thereof, alkyl substitution products, An epoxy resin selected from hydrogenated products is used.
- examples of commercially available epoxy resin [C2] include “Epiclon (registered trademark)” 830 and 806 (manufactured by DIC Corporation), “jER (registered trademark)” 152 (manufactured by Mitsubishi Chemical Corporation), and the like.
- the epoxy resin [C2] a bisphenol F-type epoxy resin having a number average molecular weight of 450 or less is preferable because it gives a high elastic modulus and has good compatibility with the epoxy resins [A2] and [B2].
- the epoxy resin [C2] is preferably contained in an amount of 10 to 40 parts by mass out of 100 parts by mass of the total epoxy resin. More preferably, the epoxy resin [C2] is contained in an amount of 20 to 40 parts by mass out of 100 parts by mass of the total epoxy resin.
- the compounding quantity of epoxy resin [C2] is less than 10 mass parts, there exists a tendency for the phase-separation structure period of the resin cured material obtained to become large.
- the compounding amount of the epoxy resin [C2] exceeds 40 parts by mass, the epoxy resins [A2] and [B2] are easily compatible with each other, and it is difficult to form a phase separation structure. Rate and toughness are likely to decrease.
- the number average molecular weight as used in the field of this invention is the value calculated
- the viscosity of the resulting epoxy resin composition can be lowered. Therefore, in the prepreg manufacturing process, the epoxy resin composition is easily impregnated between the reinforcing fibers, so that the fiber content of the obtained prepreg can be improved.
- the number average molecular weight of the epoxy resin [C2] is larger than 450, the viscosity of the epoxy resin composition tends to be high, so that the epoxy resin composition is difficult to impregnate between the reinforcing fibers in the prepreg manufacturing process. It tends to be difficult to improve the fiber content.
- the effect as a compatibilizer becomes large because the number average molecular weight of epoxy resin [C2] is 450 or less, it is easy to form a fine phase-separated structure.
- the number average molecular weight of the bisphenol F-type epoxy resin [C2] is larger than 450, the component [C2] is easily compatible with any one of the phases, so that the effect as a compatibilizer tends to be small. As a result, the phase separation structure period of the cured resin tends to increase.
- Examples of commercially available bisphenol F type epoxy resins having a number average molecular weight of 450 or less include “Epiclon (registered trademark)” 830 and 806 (manufactured by DIC Corporation).
- the curing agent [D] is the same as the curing agent [D] described in the first embodiment.
- the epoxy resin composition of the present invention contains an epoxy resin other than the epoxy resins [A] to [C] for the purpose of adjusting viscoelasticity and improving workability or the elastic modulus and heat resistance of the cured resin. It can add in the range which does not lose the effect of invention. These may be used in combination of not only one type but also a plurality of types.
- phenol novolac type epoxy resin cresol novolac epoxy resin, resorcinol type epoxy resin, phenol aralkyl type epoxy resin, dicyclopentadiene type epoxy resin, epoxy resin having biphenyl skeleton, isocyanate modified epoxy resin, anthracene type epoxy resin Polyethylene glycol type epoxy resin, N, N′-diglycidylaniline, liquid bisphenol A type epoxy resin, and the like.
- phenol novolak type epoxy resins include “Epicoat (registered trademark)” 152, 154 (above, manufactured by Mitsubishi Chemical Corporation), “Epicron (registered trademark)” N-740, N-770, N-775 ( As mentioned above, DIC Corporation) etc. are mentioned.
- cresol novolac type epoxy resins Commercial products of cresol novolac type epoxy resins include “Epiclon (registered trademark)” N-660, N-665, N-670, N-673, N-695 (above, manufactured by DIC Corporation), “EOCN ( Registered trademark) "1020, 102S, 104S (Nippon Kayaku Co., Ltd.).
- resorcinol type epoxy resin examples include “Denacol (registered trademark)” EX-201 (manufactured by Nagase ChemteX Corporation).
- dicyclopentadiene type epoxy resins include “Epiclon (registered trademark)” HP7200, HP7200L, HP7200H (above, manufactured by DIC Corporation), “TACTIX (registered trademark)” 558 (manufactured by Huntsman Advanced Materials) XD-1000-1L, XD-1000-2L (Nippon Kayaku Co., Ltd.) and the like.
- Examples of commercially available epoxy resins having a biphenyl skeleton include “Epicoat (registered trademark)” YX4000H, YX4000, YL6616 (manufactured by Mitsubishi Chemical Corporation), NC-3000 (manufactured by Nippon Kayaku Co., Ltd.), and the like. It is done.
- Examples of commercially available isocyanate-modified epoxy resins include “AER (registered trademark)” 4152 (manufactured by Asahi Kasei E-Materials Co., Ltd.) and XAC4151 (manufactured by Asahi Kasei Chemicals Co., Ltd.) having an oxazolidone ring.
- Examples of commercially available anthracene epoxy resins include YX8800 (manufactured by Mitsubishi Chemical Corporation).
- Examples of commercially available polyethylene glycol type epoxy resins include “Denacol (registered trademark)” EX810, 811, 850, 851, 821, 830, 841, 861 (manufactured by Nagase ChemteX Corporation).
- liquid bisphenol A type epoxy resins examples include “jER (registered trademark)” 828 (manufactured by Mitsubishi Chemical Corporation).
- the epoxy resin composition of the present invention has a heat-solubility soluble in an epoxy resin in order to control viscoelasticity and improve mechanical properties such as tack and drape characteristics of prepreg and impact resistance of fiber reinforced composite materials.
- Organic particles such as plastic resins, rubber particles and thermoplastic resin particles, inorganic particles, and the like can be blended.
- thermoplastic resin soluble in the epoxy resin a thermoplastic resin having a hydrogen-bonding functional group that can be expected to improve the adhesion between the resin and the reinforcing fiber is preferably used.
- the hydrogen bondable functional group include an alcoholic hydroxyl group, an amide bond, a sulfonyl group, and a carboxyl group.
- thermoplastic resin having an alcoholic hydroxyl group examples include polyvinyl acetal resins such as polyvinyl formal and polyvinyl butyral; polyvinyl alcohol and phenoxy resin.
- thermoplastic resin having an amide bond examples include polyamide, polyimide, polyamideimide, and polyvinylpyrrolidone.
- thermoplastic resin having a sulfonyl group examples include polysulfone.
- polyamide, polyimide and polysulfone may have a functional group such as an ether bond and a carbonyl group in the main chain.
- the polyamide may have a substituent on the nitrogen atom of the amide group.
- thermoplastic resin having a carboxyl group examples include polyester, polyamide, and polyamideimide.
- thermoplastic resins soluble in epoxy resins and having hydrogen-bonding functional groups include: Denkabutyral as a polyvinyl acetal resin; “Denkapoval (registered trademark)” as a polyvinyl alcohol resin (manufactured by Denki Kagaku Kogyo Co., Ltd.) , “Vinylec (registered trademark)” (manufactured by JNC); “Macromelt (registered trademark)” (manufactured by Henkel Co., Ltd.), “Amilan (registered trademark)” CM4000 (manufactured by Toray Industries, Inc.); polyimide As “Ultem (registered trademark)” (manufactured by Subic Innovative Plastics), “Aurum (registered trademark)” (manufactured by Mitsui Chemicals), “Vespel (registered trademark)” (manufactured by DuPont); “Victrex (registered trademark)” (registere
- the acrylic resin has high compatibility with the epoxy resin and is preferably used for controlling the viscoelasticity.
- Commercially available acrylic resins include “Dianar (registered trademark)” BR series (Mitsubishi Rayon Co., Ltd.), “Matsumoto Microsphere (registered trademark)” M, M100, M500 (Matsumoto Yushi Seiyaku Co., Ltd.) ) And the like.
- cross-linked rubber particles, and core-shell rubber particles obtained by graft polymerization of a different polymer on the surface of the cross-linked rubber particles are preferably used from the viewpoint of handleability and the like.
- Examples of commercially available core-shell rubber particles include “Paraloid (registered trademark)” EXL-2655, EXL-2611, and EXL-3387 (produced by Rohm and Haas Co., Ltd.) made of a butadiene / alkyl methacrylate / styrene copolymer.
- thermoplastic resin particles polyamide particles or polyimide particles are preferably used.
- polyamide particles SP-500 (manufactured by Toray Industries, Inc.), “Orgazol (registered trademark)” (manufactured by Arkema Co., Ltd.) and the like can be used.
- At least one block copolymer [E] (hereinafter abbreviated to block copolymer [E]) selected from the group consisting of SBM, BM, and MBM Further, it is effective to improve toughness and impact resistance while maintaining excellent heat resistance of the epoxy resin composition.
- S, B, and M mean each block defined below.
- Each block represented by S, B and M is linked directly by a covalent bond or through some chemical structure.
- any block of S, B, and M is used.
- the block copolymer is BM or MBM, B and M are used. It is preferable from the viewpoint of improving toughness that any of the blocks is compatible with the epoxy resin.
- Block M is a block made of a polymethyl methacrylate homopolymer or a copolymer containing 50% by mass or more of methyl methacrylate.
- the block M is preferably composed of 60% by mass or more of syndiotactic PMMA (polymethyl methacrylate).
- Block B is a block that is incompatible with block M and has a glass transition temperature of 20 ° C. or lower.
- the glass transition temperature of the block B is a dynamic viscoelasticity measuring device (RSAII: manufactured by Rheometrics, Inc. or rheometer ARES: whether the epoxy resin composition or the block copolymer [E] alone is used.
- Rheometrics, Inc. or rheometer ARES whether the epoxy resin composition or the block copolymer [E] alone is used.
- TA Instruments can be measured by the DMA method. That is, the measurement sample is made into a plate having a thickness of 1 mm, a width of 2.5 mm, and a length of 34 mm, and the period for applying stress is measured while sweeping it at a temperature of ⁇ 100 to 250 ° C., and its tan ⁇ value is measured.
- the sample is manufactured as follows. When an epoxy resin composition is used, the uncured resin composition is defoamed in vacuum, and then 130 mm in a mold set to a thickness of 1 mm by a 1 mm thick “Teflon (registered trademark)” spacer. By curing at a temperature of 2 ° C. for 2 hours, a cured resinous plate-like resin can be obtained. When a block copolymer is used alone, a void-free plate is prepared using a biaxial extruder. These plates can be evaluated by cutting them into the above size with a diamond cutter.
- the glass transition temperature of block B is 20 ° C. or lower, preferably 0 ° C. or lower, more preferably ⁇ 40 ° C. or lower.
- the glass transition temperature is preferably as low as possible from the viewpoint of toughness. However, if the glass transition temperature is lower than ⁇ 100 ° C., there may be a problem in workability such as a roughened cutting surface when a fiber-reinforced composite material is obtained.
- the block B is preferably an elastomer block.
- the monomer constituting such an elastomer block can be selected from butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene and 2-phenyl-1,3-butadiene.
- the block B is preferably selected from polydienes, particularly polybutadiene, polyisoprene and random copolymers thereof, or partially or completely hydrogenated polydienes from the viewpoint of toughness.
- polydienes particularly polybutadiene, polyisoprene and random copolymers thereof, or partially or completely hydrogenated polydienes from the viewpoint of toughness.
- Such partially or fully hydrogenated polydienes can be made according to conventional hydrogenation methods.
- 1,4-polybutadiene (glass transition temperature of about -90 ° C.) having the lowest glass transition temperature. This is because the use of the block B having a lower glass transition temperature is advantageous from the viewpoint of impact resistance and toughness.
- alkyl (meth) acrylate can also be used as the monomer constituting the elastomer block B.
- alkyl (meth) acrylate can also be used.
- Specific examples include ethyl acrylate ( ⁇ 24 ° C.), butyl acrylate ( ⁇ 54 ° C.), 2-ethylhexyl acrylate ( ⁇ 85 ° C.), hydroxyethyl acrylate ( ⁇ 15 ° C.), and 2-ethylhexyl methacrylate ( ⁇ 10 ° C.).
- the numerical value shown in parentheses after the name of each acrylate is the glass transition temperature of the block B obtained when each acrylate is used. Of these, butyl acrylate is preferably used.
- the block B is more preferably selected from poly 1,4-butadiene, polybutyl acrylate and poly (2-ethylhexyl acrylate), and more preferably poly 1,4-butadiene or poly (butyl acrylate).
- Block S is a block that is incompatible with blocks B and M and has a glass transition temperature higher than that of block B.
- the glass transition temperature or melting point of the block S is preferably 23 ° C. or higher, and more preferably 50 ° C. or higher.
- monomers constituting the block S include aromatic vinyl compounds such as styrene, ⁇ -methylstyrene or vinyl toluene; alkyl esters of (meth) acrylic acid having an alkyl chain having 1 to 18 carbon atoms. it can.
- the blending amount of the block copolymer [E] is preferably 1 to 10 parts by mass, more preferably 100 parts by mass with respect to 100 parts by mass of all epoxy resin components, from the viewpoint of mechanical properties and compatibility with the composite production process. Is 2 to 7 parts by mass.
- the blending amount of the block copolymer [E] is less than 1 part by mass, the effect of improving the toughness and plastic deformation ability of the cured resin is small, and the impact resistance of the fiber-reinforced composite material may be lowered.
- the elastic modulus of the cured resin is lowered, the mechanical properties of the fiber-reinforced composite material are lowered, and the viscosity of the epoxy resin composition is increased, so that the handleability may be deteriorated.
- the two blocks M of the triblock copolymer MBM may be the same as or different from each other. Also, the molecular weight can be different due to the same monomer.
- the block M of the triblock copolymer MBM is diblock copolymer.
- the M block of the polymer BM may be the same as or different from the M block, and the block B of the MBM triblock may be the same as or different from the diblock copolymer BM.
- the triblock copolymer SBM and the diblock copolymer BM and / or the triblock copolymer MBM are used in combination as the block copolymer [E], the triblock The block M of the copolymer SBM, each block M of the triblock copolymer MBM, and the block M of the diblock copolymer BM may be the same as or different from each other.
- the blocks B of the triblock copolymer SBM, the triblock copolymer MBM, and the diblock copolymer BM may be the same as or different from each other.
- the block copolymer [E] can be produced by anionic polymerization.
- it can be produced by the methods described in European Patent No. EP 524,054 and European Patent No. EP 749,987.
- triblock copolymer MBM examples include Nanostrength M22 (manufactured by Arkema) consisting of methyl methacrylate-butyl acrylate-methyl methacrylate and Nanostrength M22N (manufactured by Arkema) having polar functional groups. Can be mentioned.
- Specific examples of the triblock copolymer SBM are Nanostrength 123, Nanostrength 250, Nanostrength 012, Nanostrength E20, Nanostrength E40 (manufactured by Arkema, Inc.) made of Arkema, which is made of styrene-butadiene-methyl methacrylate. Is mentioned.
- the epoxy resin composition comprising the epoxy resins [A2] to [C2], the curing agent [D] and the block copolymer [E] has a cured resin obtained by the epoxy resin [A2] rich phase, the epoxy resin [B2 ] Having a phase separation structure including a rich phase and a block copolymer [E] rich phase, an epoxy resin [A2] rich phase, an epoxy resin [B2] rich phase, and a block copolymer [E] rich phase
- the phase separation structure period is preferably 1 nm to 1 ⁇ m.
- the epoxy resin composition comprising the epoxy resins [A1] to [C1], the curing agent [D] and the block copolymer [E] has a cured resin obtained by the epoxy resin [A1] rich phase and the epoxy resin [B1. ] Having a phase separation structure containing a rich phase and a block copolymer [E] rich phase, and comprising an epoxy resin [A1] rich phase, an epoxy resin [B1] rich phase, and a block copolymer [E] rich phase.
- the phase separation structure period is preferably 1 nm to 5 ⁇ m, and the phase separation period of the block copolymer [E] rich phase is more preferably 1 nm to 1 ⁇ m.
- phase separation structure period of the epoxy resin [A] rich phase and the epoxy resin [B] rich phase is too small, one or more of the following adjustment methods are within the range not impairing the object of the present invention.
- the phase separation structure period can be increased. (1) The blending ratio of the epoxy resin [C] to the total epoxy resin is reduced. (2) Increase the softening point of the epoxy resin [A]. (3) Lower the softening point of the epoxy resin [B]. (4) Increase the blending ratio of both epoxy resins [A] and [B].
- the phase separation structure period of the epoxy resin [A] rich phase and the epoxy resin [B] rich phase is within a range that does not impair the object of the present invention, and one or more of the following adjustment methods are performed. Therefore, it can be reduced.
- (1) Increase the blending ratio of the epoxy resin [C] to the total epoxy resin.
- (2) Lower the softening point of the epoxy resin [A].
- (3) Increase the softening point of the epoxy resin [B].
- the blending ratio of both epoxy resins [A] and [B] is reduced.
- phase separation structure period of the block copolymer [E] rich phase can be reduced by performing one or more of the following adjustment methods within a range that does not impair the object of the present invention. it can.
- phase separation structure period of the block copolymer [E] rich phase can be increased by performing one or more of the following adjustment methods within a range that does not impair the object of the present invention. .
- the viscosity at 80 ° C. of the epoxy resin composition is preferably 0.5 to 200 Pa ⁇ s from the viewpoint of processability such as tack and drape. .
- the viscosity at 80 ° C. of the epoxy resin composition is less than 0.5 Pa ⁇ s, the produced prepreg is difficult to maintain its shape, and the prepreg may be cracked.
- many resin flows are produced at the time of molding of the fiber reinforced composite material, and there is a possibility that the reinforced fiber content varies. Further, when the viscosity at 80 ° C.
- the viscosity at 80 ° C. of the epoxy resin composition is more preferably in the range of 5 to 50 Pa ⁇ s because the resin can easily be impregnated between the reinforcing fibers in the prepreg manufacturing process and a prepreg having a high fiber content can be manufactured. .
- the viscosity can be lowered by performing one or more of the following methods (1) to (2) within the range not impairing the object of the present invention, and the following (3) to (4)
- the viscosity can be increased by performing one or more methods.
- (1) Use epoxy resin [A] and / or [B] having a low softening point.
- (2) Increase the amount of the epoxy resin [C].
- (3) An epoxy resin [A] and / or [B] having a high softening point is used.
- a thermoplastic resin is blended.
- the viscosity is a dynamic viscoelasticity measuring device (Rheometer RDA2: manufactured by Rheometrics or Rheometer ARES: manufactured by TA Instruments), a parallel plate having a diameter of 40 mm, and a temperature rising rate of 1. It refers to the complex viscoelastic modulus ⁇ * obtained by simply raising the temperature at 5 ° C./min and measuring at a frequency of 0.5 Hz and a gap of 1 mm.
- the elastic modulus of the cured resin product is preferably in the range of 3.8 to 5.0 GPa. More preferably, it is 4.0 to 5.0 GPa.
- the elastic modulus is less than 3.8 GPa, the static strength of the obtained fiber-reinforced composite material may be lowered.
- this elastic modulus exceeds 5.0 GPa, the plastic deformation ability of the obtained fiber reinforced composite material tends to be low, and the impact strength of the fiber reinforced composite material may be reduced. The method for measuring the elastic modulus will be described in detail later.
- the elastic modulus of the cured resin can be improved by performing one or more of the following methods within a range that does not impair the object of the present invention.
- a bisphenol F type epoxy resin having a high elastic modulus is used as the epoxy resin [A].
- (3) An amine type epoxy is used as the epoxy resin [B], and an aminophenol type epoxy resin having a high elastic modulus is used.
- (4) A bisphenol F type epoxy resin is used as the epoxy resin [C].
- the curing temperature and curing time for obtaining the cured resin are selected according to the curing agent and catalyst to be blended.
- the curing agent and catalyst for example, in the case of a curing agent system in which dicyandiamide and DCMU are combined, conditions for curing at a temperature of 130 to 150 ° C. for 90 minutes to 2 hours are preferable, and when diaminodiphenyl sulfone is used, a temperature of 180 ° C. for 2 to 3 hours. Conditions for curing are preferred.
- the resin toughness value of the cured resin obtained by curing the epoxy resin composition of the present invention is preferably 1.1 MPa ⁇ m 0.5 or more. More preferably, it is 1.3 MPa ⁇ m 0.5 or more. If the resin toughness value is less than 1.1 MPa ⁇ m 0.5 , the impact resistance of the resulting fiber-reinforced composite material may be reduced. The method for measuring the resin toughness value will be described in detail later.
- the resin toughness value can be improved by performing one or more of the following methods within a range that does not impair the object of the present invention.
- An epoxy resin [A] and / or [B] having a large number average molecular weight is used.
- a kneader, a planetary mixer, a three-roll extruder, a twin-screw extruder, or the like is preferably used.
- the epoxy resins [A] to [C] are added, and the temperature of the epoxy resin mixture is increased to an arbitrary temperature of 130 to 180 ° C. while stirring to dissolve the epoxy resins [A] to [C] uniformly.
- other components such as the block copolymer [E] other than the curing agent [D] and the curing accelerator may be added and kneaded together.
- the temperature is preferably lowered to 100 ° C. or lower, more preferably 80 ° C. or lower, and further preferably 60 ° C. or lower, and the curing agent [D] and the curing accelerator are added, kneaded and dispersed.
- This method is preferably used because an epoxy resin composition having excellent storage stability can be obtained.
- the fiber-reinforced composite material containing the cured product of the epoxy resin composition of the present invention as a matrix resin can be obtained by impregnating the epoxy resin composition of the present invention into a reinforcing fiber and then curing.
- the reinforcing fiber used in the present invention is not particularly limited, and glass fiber, carbon fiber, aramid fiber, boron fiber, alumina fiber, silicon carbide fiber and the like are used. Two or more of these fibers may be mixed and used. Among these, it is preferable to use carbon fibers from which a lightweight and highly rigid fiber-reinforced composite material can be obtained. Among these, carbon fibers having a tensile modulus of 230 to 800 GPa are preferably used, and carbon fibers having a tensile modulus of 280 GPa are more preferably used.
- the form of the reinforcing fiber is not particularly limited, and for example, long fibers arranged in one direction, tows, woven fabrics, mats, knits, braids, short fibers chopped to a length of less than 10 mm, and the like are used.
- the term “long fiber” as used herein refers to a single fiber or fiber bundle that is substantially continuous by 10 mm or more.
- a short fiber is a fiber bundle cut to a length of less than 10 mm.
- an array in which reinforcing fiber bundles are aligned in a single direction is most suitable.
- the method for producing the fiber-reinforced composite material of the present invention is not particularly limited, but includes a prepreg lamination molding method, a resin transfer molding method, a resin film infusion method, a hand layup method, a sheet molding compound method, and a filament winding method. , Pultrusion method, etc.
- the resin transfer molding method is a method in which a reinforcing fiber base material is directly impregnated with a liquid thermosetting resin composition and then cured. Since this method does not go through an intermediate such as a prepreg, it has the potential to reduce molding costs, and can be preferably used for structural materials such as spacecraft, aircraft, railway vehicles, automobiles, and ships.
- the prepreg laminate molding method is to form and / or laminate a prepreg impregnated with a thermosetting resin composition on a reinforcing fiber substrate, and then heat cure the resin while applying pressure to the shaped product and / or laminate.
- a fiber reinforced composite material is obtained.
- the filament winding method 1 to several tens of rovings of reinforcing fibers are arranged, wound around a rotating mold (mandrel) while impregnated with a thermosetting resin composition, tensioned to a predetermined thickness and wound at a predetermined angle, This is a method of demolding after curing.
- reinforcing fibers are continuously passed through an impregnation tank filled with a liquid thermosetting resin composition to impregnate the thermosetting resin composition, and then continuously by a squeeze die and a heating mold by a tension machine.
- This is a method of forming and curing while pulling out. Since this method has an advantage that a fiber reinforced composite material can be continuously formed, it is used for manufacturing reinforced fiber plastics (FRP) such as fishing rods, rods, pipes, sheets, antennas, and building structures.
- FRP reinforced fiber plastics
- the prepreg laminate molding method is preferable because the obtained fiber-reinforced composite material is excellent in rigidity and strength.
- a preferred prepreg includes the epoxy resin composition of the present invention and reinforcing fibers. Such a prepreg can be obtained by impregnating the reinforcing fiber substrate with the epoxy resin composition of the present invention. Examples of the impregnation method include a wet method and a hot melt method (dry method).
- the reinforcing fiber is pulled up, and the solvent is evaporated from the reinforcing fiber using an oven or the like.
- the hot melt method is a method in which a reinforcing fiber is impregnated directly with an epoxy resin composition whose viscosity is reduced by heating, or a film in which an epoxy resin composition is coated on a release paper is prepared, and then both sides of the reinforcing fiber are prepared.
- it is a method of impregnating a reinforcing fiber with a resin by overlapping the film from one side and heating and pressing. Since there is no solvent remaining in the prepreg, it is preferable to use a hot melt method.
- the amount of reinforcing fibers per unit area of the prepreg is preferably 70 to 200 g / m 2 .
- the mass content of the reinforcing fiber in the prepreg is preferably 60 to 90% by mass, more preferably 65 to 85% by mass, and further preferably 70 to 80% by mass.
- the mass content of the reinforced fiber is less than 60% by mass, the resin ratio is too large, so that it is difficult to obtain the advantages of the fiber reinforced composite material having excellent specific strength and specific elastic modulus, or when the fiber reinforced composite material is cured.
- the calorific value may be too high.
- the mass content of the reinforcing fiber exceeds 90% by mass, the resin is difficult to be impregnated, so that the obtained fiber-reinforced composite material may have a lot of voids.
- a press molding method as a method of applying heat and pressure, a press molding method, an autoclave molding method, a bagging molding method, a wrapping tape method, an internal pressure molding method, or the like can be appropriately used.
- the autoclave molding method is a method in which a prepreg is laminated on a tool plate having a predetermined shape, covered with a bagging film, and pressurized and heat-cured while degassing the inside of the laminate. Since the fiber orientation can be precisely controlled and the generation of voids is small, a molded article having excellent mechanical properties and high quality can be obtained.
- the pressure applied during molding is preferably 0.3 to 1.0 MPa.
- the molding temperature is preferably in the range of 90 to 200 ° C.
- the wrapping tape method is a method of forming a tubular body made of a fiber reinforced composite material by winding a prepreg around a mandrel or the like. This is a preferable method when producing rod-shaped bodies such as golf shafts and fishing rods. More specifically, the prepreg is wound around a mandrel, and in order to fix and apply pressure to the prepreg, a wrapping tape made of a thermoplastic film is wound around the wound prepreg while applying tension, and pressure is applied to the prepreg. After the resin is heat-cured in an oven, the mandrel is withdrawn to obtain a tubular body.
- the tension for winding the wrapping tape is preferably 20 to 78N.
- the molding temperature is preferably in the range of 80 to 200 ° C.
- the internal pressure molding method is to set a preform in which a prepreg is wound on an internal pressure applying body such as a tube made of a thermoplastic resin in a mold, and then introduce a high pressure gas into the internal pressure applying body to apply pressure. At the same time, the mold is heated and molded.
- This method is preferably used when molding a complicated shape such as a golf shaft, a bad, a racket such as tennis or badminton.
- the pressure applied during molding is preferably 0.1 to 2.0 MPa.
- the molding temperature is preferably in the range of room temperature to 200 ° C, more preferably in the range of 80 to 180 ° C.
- the cured product of the epoxy resin composition of the present invention and a fiber-reinforced composite material containing reinforcing fibers are preferably used for sports applications, general industrial applications, and aerospace applications. More specifically, in sports applications, it is preferably used for golf shafts, fishing rods, tennis or badminton rackets, hockey sticks, ski poles, and the like. In addition, in general industrial applications, structural materials for moving bodies such as automobiles, bicycles, ships and railway vehicles, drive shafts, leaf springs, windmill blades, pressure vessels, flywheels, paper rollers, roofing materials, cables, and repair reinforcement materials Etc. are preferably used.
- the tubular body made of fiber reinforced composite material obtained by curing the prepreg of the present invention into a tubular shape can be preferably used for golf shafts, fishing rods and the like.
- SBM copolymer (“Nanostrength®” E40: S is polystyrene (Tg: about 90 ° C.), B is poly 1,4-butadiene (Tg: about ⁇ 90 ° C.), M is poly Block copolymer consisting of methyl methacrylate (Tg: about 130 ° C., manufactured by Arkema Co., Ltd.) MBM copolymer ("Nanostrength (registered trademark)" M22N: B is polybutyl acrylate (Tg: about -50 ° C), M is polar methacrylate having higher SP value than methyl methacrylate and methyl methacrylate A block copolymer comprising a copolymer of group-containing monomers (Tg: about 130 ° C., manufactured by Arkema Co., Ltd.).
- HLC Number average molecular weight measurement “HLC (registered trademark)” 8220GPC (manufactured by Tosoh Corporation) as a measuring device, UV-8000 (254 nm) as a detector, and TSK-G4000H (manufactured by Tosoh Corporation) as a column.
- the epoxy resin to be measured was dissolved in THF at a concentration of 0.1 mg / ml, and this was measured at a flow rate of 1.0 ml / min and a temperature of 40 ° C.
- the retention time of the measurement sample was converted to molecular weight using the retention time of the polystyrene calibration sample, and the number average molecular weight was determined.
- the initial precrack was introduced into the test piece by applying a razor blade cooled to liquid nitrogen temperature to the test piece and applying an impact to the razor with a hammer.
- the resin toughness value refers to the critical stress strength of deformation mode I (opening type).
- phase separation structure is a biphasic continuous structure
- draw three straight lines of a predetermined length on the micrograph extract the intersection of the straight line and the phase interface, measure the distance between the adjacent intersections, These number average values were used as the structure period.
- the predetermined length is set as follows based on a micrograph.
- the structural period is expected to be on the order of 0.01 ⁇ m (0.01 ⁇ m or more and less than 0.1 ⁇ m)
- a sample photograph was taken at a magnification of 20,000 times, and a length of 20 mm drawn on the photograph (1 ⁇ m on the sample) was defined as a predetermined straight line length.
- phase separation structure period is expected to be on the order of 0.1 ⁇ m (0.1 ⁇ m or more and less than 1 ⁇ m)
- a photograph is taken at a magnification of 2,000 times and a length of 20 mm on the photograph (10 ⁇ m on the sample)
- the length is a predetermined length of the straight line.
- the phase separation structure period is expected to be on the order of 1 ⁇ m (1 ⁇ m or more and less than 10 ⁇ m)
- a photograph is taken at a magnification of 200 times, and a length of 20 mm on the photograph (a length of 100 ⁇ m on the sample) is defined as a predetermined straight line length. did. If the measured phase separation structure period was out of the expected order, it was measured again at a magnification corresponding to the corresponding order.
- the phase separation structure is a sea-island structure
- three predetermined regions on the micrograph were selected at random, the island phase size in the region was measured, and the number average value thereof was taken as the structure period.
- the size of the island phase refers to the length of the shortest distance line drawn from the phase interface to one phase interface through the island phase. Even when the island phase is an ellipse, an indeterminate shape, or a circle or ellipse of two or more layers, the shortest distance passing through the island phase from the phase interface to one phase interface is defined as the island phase size.
- the predetermined region is set as follows based on a micrograph.
- phase separation structure period When the phase separation structure period is expected to be on the order of 0.01 ⁇ m (0.01 ⁇ m or more and less than 0.1 ⁇ m), a photograph of the sample was taken at a magnification of 20,000 times, and an area of 4 mm square on the photograph (0 on the sample) .2 ⁇ m square area) was defined as a predetermined area.
- a sample photograph is taken at a magnification of 2,000 times, and a 4 mm square area (sample) The upper 2 ⁇ m square area) was defined as a predetermined area.
- phase separation structure period When the phase separation structure period is expected to be on the order of 1 ⁇ m (1 ⁇ m or more and less than 10 ⁇ m), a photograph was taken at a magnification of 200 times, and an area of 4 mm square on the photograph (an area of 20 ⁇ m square on the sample) was defined as a predetermined area. If the measured phase separation structure period was out of the expected order, it was measured again at a magnification corresponding to the corresponding order.
- T700SC-24K manufactured by Toray Industries, Inc., tensile elastic modulus: 230 GPa, tensile strength: 4900 MPa
- the mass of carbon fiber per unit area was 125 g / m 2
- a unidirectional prepreg using T700SC having a fiber mass content of 75% by mass was also produced.
- a wrapping tape heat-resistant film tape
- the width of the wrapping tape was 15 mm
- the tension was 34 N
- the winding pitch (deviation amount at the time of winding) was 2.0 mm
- E WR [(cos ⁇ cos ⁇ ) ⁇ (cos ⁇ ′ ⁇ cos ⁇ ) ( ⁇ + ⁇ ) / ( ⁇ + ⁇ ′)]
- J Absorbed energy
- WR Moment around the rotation axis of the hammer (N ⁇ m)
- ⁇ Hammer lift angle (°)
- ⁇ ' Swing angle when the hammer is swung from the lift angle ⁇ (°)
- ⁇ Hammer swing angle after test specimen breakage (°)
- the 0 ° bending strength of the unidirectional laminated plate was measured as an index of bending strength of the fiber reinforced composite material.
- a test piece was cut out of the unidirectional laminate so as to have a thickness of 2 mm, a width of 15 mm, and a length of 100 mm.
- the test piece was measured at a crosshead speed of 5.0 mm / min, a span of 80 mm, an indenter diameter of 10 mm, and a fulcrum diameter of 4 mm, and the bending strength was calculated.
- the obtained bending strength was converted into Vf60%.
- Example 1 40 parts of jER1007 as epoxy resin [A1] or [A2], 20 parts of jER630 as epoxy resin [B1] or [B2], 40 parts of Epicron 830 as epoxy resin [C1] or [C2], curing agent [D ]
- An epoxy resin composition was prepared using DICY7 as an amount of 0.9 equivalent of active hydrogen groups with respect to the epoxy groups of all epoxy resin components and 2 parts of DCMU99 as a curing accelerator.
- the resulting resin composition had a good viscosity at 80 ° C.
- the resulting epoxy resin composition was heated at 2.5 ° C./min and cured at 130 ° C. for 90 minutes.
- the obtained cured resin formed a fine phase separation structure and had good mechanical properties.
- Epoxy resin compositions were prepared in the same manner as in Example 1 except that the compositions shown in Tables 2 to 5 were changed. The evaluation results are shown in Tables 2-5.
- the cured resin obtained from the epoxy resin composition of each example formed a fine phase separation structure and had good mechanical properties. Moreover, the impact resistance property and the 0 ° bending strength of the unidirectional laminate were good for the tubular body made of fiber-reinforced composite material produced using the prepreg composed of the epoxy resin composition and carbon fiber obtained.
- the obtained cured resin formed a uniform phase separation structure and lacked the elastic modulus. Furthermore, since the viscosity at 80 ° C. of the epoxy resin composition exceeded 200 Pa ⁇ s, voids occurred in the fiber-reinforced composite material. As a result, the 0 ° bending strength of the unidirectional laminate produced using the obtained epoxy resin composition and carbon fiber was insufficient.
- the epoxy resin composition of the present invention has a high elastic modulus and high toughness, and further has a low viscosity, so that it enables prepreg molding with a high fiber content.
- strength can be obtained by combining an epoxy resin composition and a reinforced fiber.
- the fiber-reinforced composite material obtained is preferably used for sports applications, general industrial applications, and aircraft applications.
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Abstract
Description
エポキシ樹脂[A1]、エポキシ樹脂[B1]、エポキシ樹脂[C1]および硬化剤[D]を含むエポキシ樹脂組成物であって、[A1]は軟化点が90℃以上のビスフェノール型エポキシ樹脂、[B1]は3官能以上のアミン型エポキシ樹脂、そして[C1]数平均分子量450以下のビスフェノールF型エポキシ樹脂であり、かつ、エポキシ樹脂[A1]~[C1]が全エポキシ樹脂成分100質量部に対して、[A1]20~50質量部、[B1]30~50質量部および[C1]10~40質量部の配合比を満たす、エポキシ樹脂組成物。
(2)エポキシ樹脂[A2]、エポキシ樹脂[B2]、エポキシ樹脂[C2]および硬化剤[D]を含み、かつ、以下の条件(1)~(4)を満たすエポキシ樹脂組成物:
また、本発明の別の態様は、エポキシ樹脂[B2]を硬化剤[D]と反応し硬化させて得られる樹脂硬化物[B2’]のSP値が、エポキシ樹脂[A2]および[C2]をそれぞれ硬化剤[D]と反応し硬化させて得られる樹脂硬化物[A2’]および[C2’]のいずれのSP値に対してよりも1.2以上大きい;
(2)エポキシ樹脂[A2]の軟化点が90℃以上であり、かつエポキシ樹脂[B2]と[C2]の軟化点がいずれも50℃以下である;
(3)エポキシ樹脂[C2]と、エポキシ樹脂[C2]のエポキシ基に対し活性水素基が0.9当量のジシアンジアミドと、エポキシ樹脂[C2]100質量部に対して2質量部の3-(3,4-ジクロロフェニル)-1,1-ジメチルウレアからなるエポキシ樹脂組成物を、室温から130℃まで2.5℃/分で昇温し、130℃で90分間反応させて得られる樹脂硬化物の弾性率が、3.5GPa以上である;および
(4)エポキシ樹脂組成物を硬化させて得られる樹脂硬化物が、[A2]リッチ相と[B2]リッチ相を含む相分離構造を有し、その相分離構造周期が1nm~1μmである。
また、本発明は、上記のエポキシ樹脂組成物と強化繊維を含むプリプレグを含む。
また、本発明は、上記のプリプレグを硬化させてなる繊維強化複合材料を含む。
また、本発明は、上記のエポキシ樹脂組成物の硬化物と、強化繊維を含む繊維強化複合材料を含む。 As a result of intensive studies to solve the above problems, the present inventors have found an epoxy resin composition having the following constitution, and have completed the present invention. That is, this invention consists of the following structures.
An epoxy resin composition comprising an epoxy resin [A1], an epoxy resin [B1], an epoxy resin [C1] and a curing agent [D], wherein [A1] is a bisphenol type epoxy resin having a softening point of 90 ° C. or higher, [ B1] is a tri- or higher functional amine type epoxy resin, and [C1] a bisphenol F type epoxy resin having a number average molecular weight of 450 or less, and the epoxy resins [A1] to [C1] are contained in 100 parts by mass of all epoxy resin components. On the other hand, an epoxy resin composition satisfying a compounding ratio of [A1] 20 to 50 parts by mass, [B1] 30 to 50 parts by mass and [C1] 10 to 40 parts by mass.
(2) Epoxy resin composition containing epoxy resin [A2], epoxy resin [B2], epoxy resin [C2] and curing agent [D] and satisfying the following conditions (1) to (4):
In another aspect of the present invention, the SP value of the cured resin [B2 ′] obtained by reacting and curing the epoxy resin [B2] with the curing agent [D] has epoxy resins [A2] and [C2]. Is larger by 1.2 or more than the SP value of any of the cured resin products [A2 ′] and [C2 ′] obtained by reacting and curing with the curing agent [D];
(2) The softening point of the epoxy resin [A2] is 90 ° C. or higher, and the softening points of the epoxy resins [B2] and [C2] are both 50 ° C. or lower;
(3) Epoxy resin [C2], dicyandiamide having an active hydrogen group of 0.9 equivalent to the epoxy group of epoxy resin [C2], and 2 parts by mass of 3- (3) to 100 parts by mass of epoxy resin [C2] Cured resin obtained by heating an epoxy resin composition comprising 3,4-dichlorophenyl) -1,1-dimethylurea from room temperature to 130 ° C. at a rate of 2.5 ° C./min and reacting at 130 ° C. for 90 minutes. And (4) a cured resin obtained by curing the epoxy resin composition has a phase separation structure including [A2] rich phase and [B2] rich phase. The period of the phase separation structure is 1 nm to 1 μm.
Moreover, this invention contains the prepreg containing said epoxy resin composition and a reinforced fiber.
Moreover, this invention contains the fiber reinforced composite material formed by hardening said prepreg.
Moreover, this invention contains the hardened | cured material of said epoxy resin composition, and the fiber reinforced composite material containing a reinforced fiber.
(1)エポキシ樹脂[B2]を硬化剤[D]と反応し硬化させて得られる樹脂硬化物[B2’]のSP値が、エポキシ樹脂[A2]および[C2]をそれぞれ硬化剤[D]と反応し硬化させて得られる樹脂硬化物[A2’]および[C2’]のいずれのSP値に対してよりも1.2以上大きい;
(2)エポキシ樹脂[A2]の軟化点が90℃以上であり、かつエポキシ樹脂[B2]と[C2]の軟化点がいずれも50℃以下である;
(3)エポキシ樹脂[C2]と、エポキシ樹脂[C2]のエポキシ基に対して活性水素基が0.9当量のジシアンジアミドと、エポキシ樹脂[C2]100質量部に対して2質量部の3-(3,4-ジクロロフェニル)-1,1-ジメチルウレア(以下、DCMUと呼ぶ)からなるエポキシ樹脂組成物を、室温から130℃まで2.5℃/分で昇温し、130℃で90分間反応させて得られる樹脂硬化物の弾性率が、3.5GPa以上である;および
(4)エポキシ樹脂[A2]~[C2]を硬化剤[D]と反応し硬化させて得られる樹脂硬化物が、[A2]リッチ相と[B2]リッチ相を含む相分離構造を有し、その相分離構造周期が1nm~1μmである。 The second embodiment of the epoxy resin composition of the present invention comprises an epoxy resin [A2], an epoxy resin [B2], an epoxy resin [C2] and a curing agent [D], and the following conditions (1) to ( An epoxy resin composition satisfying 4):
(1) The SP value of the cured resin [B2 ′] obtained by reacting the epoxy resin [B2] with the curing agent [D] and curing the epoxy resin [A2] and [C2] is the curing agent [D]. Greater than the SP value of any of the cured resin products [A2 ′] and [C2 ′] obtained by reacting with and curing the resin;
(2) The softening point of the epoxy resin [A2] is 90 ° C. or higher, and the softening points of the epoxy resins [B2] and [C2] are both 50 ° C. or lower;
(3) Epoxy resin [C2], dicyandiamide having an active hydrogen group of 0.9 equivalent to the epoxy group of epoxy resin [C2], and 2 parts by mass of 3-parts of epoxy resin [C2] with respect to 100 parts by mass. An epoxy resin composition comprising (3,4-dichlorophenyl) -1,1-dimethylurea (hereinafter referred to as DCMU) was heated from room temperature to 130 ° C. at a rate of 2.5 ° C./min and then at 130 ° C. for 90 minutes. The elastic modulus of the cured resin obtained by reacting is 3.5 GPa or more; and (4) The cured resin obtained by reacting and curing the epoxy resins [A2] to [C2] with the curing agent [D]. However, it has a phase separation structure including [A2] rich phase and [B2] rich phase, and the phase separation structure period is 1 nm to 1 μm.
(1) ([B2’]のSP値)≧([A2’]のSP値)+1.2
(2) ([B2’]のSP値)≧([C2’]のSP値)+1.2
ここで、SP値とは、一般に知られている溶解性パラメータのことであり、溶解性および相溶性の指標となる。本発明で規定されるSP値は、Polym.Eng.Sci.,14(2),147-154(1974)に記載された、Fedorsの方法に基づき、分子構造から算出した値である。[B2’]のSP値が、[A2’]のSP値に1.2を足した値より小さい場合は、得られる樹脂硬化物中で、[A2]が[B2]と相溶し、均一構造になるため、樹脂硬化物の弾性率と靱性が十分でない。また、[B2’]のSP値が、[C2’]のSP値に1.2を足した値より小さい場合は、得られる樹脂硬化物中で、相溶化剤である[C2]が[B2]のみに溶け込むため、[A2]リッチ相と[B2]リッチ相の粗大相分離を引き起こす。 In this embodiment, the cured resin products [A2 ′], [B2 ′], and [C2 ′ obtained by reacting the epoxy resins [A2], [B2], and [C2] with the curing agent [D], respectively. ] Must satisfy the following condition.
(1) (SP value of [B2 ′]) ≧ (SP value of [A2 ′]) + 1.2
(2) (SP value of [B2 ′]) ≧ (SP value of [C2 ′]) + 1.2
Here, the SP value is a generally known solubility parameter, and is an index of solubility and compatibility. The SP value defined in the present invention is Polym. Eng. Sci. , 14 (2), 147-154 (1974), and calculated from the molecular structure based on the Fedors method. When the SP value of [B2 ′] is smaller than the value obtained by adding 1.2 to the SP value of [A2 ′], [A2] is compatible with [B2] in the obtained cured resin and is uniform. Since it becomes a structure, the elastic modulus and toughness of the resin cured product are not sufficient. Moreover, when the SP value of [B2 ′] is smaller than the value obtained by adding 1.2 to the SP value of [C2 ′], [C2], which is a compatibilizing agent, is [B2] in the obtained cured resin. ], It causes coarse phase separation of [A2] rich phase and [B2] rich phase.
(1)全エポキシ樹脂に対するエポキシ樹脂[C]の配合割合を減らす。
(2)エポキシ樹脂[A]の軟化点を高くする。
(3)エポキシ樹脂[B]の軟化点を低くする。
(4)エポキシ樹脂[A]、[B]両方の配合割合を増やす。 When the phase separation structure period of the epoxy resin [A] rich phase and the epoxy resin [B] rich phase is too small, one or more of the following adjustment methods are within the range not impairing the object of the present invention. By carrying out the step, the phase separation structure period can be increased.
(1) The blending ratio of the epoxy resin [C] to the total epoxy resin is reduced.
(2) Increase the softening point of the epoxy resin [A].
(3) Lower the softening point of the epoxy resin [B].
(4) Increase the blending ratio of both epoxy resins [A] and [B].
(1)全エポキシ樹脂に対するエポキシ樹脂[C]の配合割合を増やす。
(2)エポキシ樹脂[A]の軟化点を低くする。
(3)エポキシ樹脂[B]の軟化点を高くする。
(4)エポキシ樹脂[A]および[B]両方の配合割合を減らす。 In addition, the phase separation structure period of the epoxy resin [A] rich phase and the epoxy resin [B] rich phase is within a range that does not impair the object of the present invention, and one or more of the following adjustment methods are performed. Therefore, it can be reduced.
(1) Increase the blending ratio of the epoxy resin [C] to the total epoxy resin.
(2) Lower the softening point of the epoxy resin [A].
(3) Increase the softening point of the epoxy resin [B].
(4) The blending ratio of both epoxy resins [A] and [B] is reduced.
(1)ブロック共重合体[E]の配合割合を減らす。
(2)エポキシ樹脂[A]の軟化点を低くする。
(3)エポキシ樹脂[B]の配合割合を増やす。 In addition, the phase separation structure period of the block copolymer [E] rich phase can be reduced by performing one or more of the following adjustment methods within a range that does not impair the object of the present invention. it can.
(1) The blending ratio of the block copolymer [E] is reduced.
(2) Lower the softening point of the epoxy resin [A].
(3) Increase the compounding ratio of the epoxy resin [B].
(1)ブロック共重合体[E]の配合割合を増やす。
(2)エポキシ樹脂[A]の軟化点を高くする。
(3)エポキシ樹脂[B]の配合割合を減らす。 In addition, the phase separation structure period of the block copolymer [E] rich phase can be increased by performing one or more of the following adjustment methods within a range that does not impair the object of the present invention. .
(1) Increase the blending ratio of the block copolymer [E].
(2) Increase the softening point of the epoxy resin [A].
(3) The blending ratio of the epoxy resin [B] is reduced.
(1)軟化点の低いエポキシ樹脂[A]および/または[B]を用いる。
(2)エポキシ樹脂[C]の配合量を増量する。
(3)軟化点の高いエポキシ樹脂[A]および/または[B]、を用いる。
(4)熱可塑樹脂を配合する。 When the epoxy resin composition of the present invention is used as a matrix resin for a prepreg, the viscosity at 80 ° C. of the epoxy resin composition is preferably 0.5 to 200 Pa · s from the viewpoint of processability such as tack and drape. . When the viscosity at 80 ° C. of the epoxy resin composition is less than 0.5 Pa · s, the produced prepreg is difficult to maintain its shape, and the prepreg may be cracked. Moreover, many resin flows are produced at the time of molding of the fiber reinforced composite material, and there is a possibility that the reinforced fiber content varies. Further, when the viscosity at 80 ° C. exceeds 200 Pa · s, the epoxy resin composition may not be sufficiently impregnated between the reinforcing fibers when the prepreg is produced. For this reason, voids are generated in the obtained fiber-reinforced composite material, and the strength of the fiber-reinforced composite material may be reduced. The viscosity at 80 ° C. of the epoxy resin composition is more preferably in the range of 5 to 50 Pa · s because the resin can easily be impregnated between the reinforcing fibers in the prepreg manufacturing process and a prepreg having a high fiber content can be manufactured. . The viscosity can be lowered by performing one or more of the following methods (1) to (2) within the range not impairing the object of the present invention, and the following (3) to (4) The viscosity can be increased by performing one or more methods.
(1) Use epoxy resin [A] and / or [B] having a low softening point.
(2) Increase the amount of the epoxy resin [C].
(3) An epoxy resin [A] and / or [B] having a high softening point is used.
(4) A thermoplastic resin is blended.
(1)エポキシ樹脂[A]として弾性率の高いビスフェノールF型エポキシ樹脂を用いる。
(2)エポキシ樹脂[B]の配合量を増やす。
(3)エポキシ樹脂[B]としてアミン型エポキシを用い、中でも弾性率の高いアミノフェノール型エポキシ樹脂を用いる。
(4)エポキシ樹脂[C]としてビスフェノールF型エポキシ樹脂を用いる。 The elastic modulus of the cured resin can be improved by performing one or more of the following methods within a range that does not impair the object of the present invention.
(1) A bisphenol F type epoxy resin having a high elastic modulus is used as the epoxy resin [A].
(2) Increase the compounding quantity of epoxy resin [B].
(3) An amine type epoxy is used as the epoxy resin [B], and an aminophenol type epoxy resin having a high elastic modulus is used.
(4) A bisphenol F type epoxy resin is used as the epoxy resin [C].
(1)数平均分子量の大きなエポキシ樹脂[A]および/または[B]、を用いる。
(2)エポキシ樹脂[A]の配合量を増やす。
(3)ブロック共重合体[E]を配合する。 The resin toughness value can be improved by performing one or more of the following methods within a range that does not impair the object of the present invention.
(1) An epoxy resin [A] and / or [B] having a large number average molecular weight is used.
(2) Increase the compounding quantity of epoxy resin [A].
(3) A block copolymer [E] is blended.
ニーダー中に、硬化剤および硬化促進剤以外の成分を所定量投入し、混練しつつ、150℃まで昇温し、150℃、1時間混練することで、透明な粘調液を得た。粘調液を70℃まで混練しつつ降温させた後、硬化剤および硬化促進剤を所定量添加して、さらに混練しエポキシ樹脂組成物を得た。各実施例および比較例の成分配合比は、表2~5に示す通りである。また、使用したエポキシ樹脂のSP値、軟化点および数平均分子量を表1に示す。 (1) Preparation of epoxy resin composition In a kneader, a predetermined amount of components other than a curing agent and a curing accelerator are added, and while kneading, the temperature is raised to 150 ° C., and kneaded at 150 ° C. for 1 hour to be transparent. A viscous liquid was obtained. After the viscous liquid was cooled to 70 ° C. while being cooled, a predetermined amount of a curing agent and a curing accelerator was added and further kneaded to obtain an epoxy resin composition. The compounding ratios of the examples and comparative examples are as shown in Tables 2 to 5. Table 1 shows the SP value, softening point, and number average molecular weight of the epoxy resin used.
・ビスフェノールA型エポキシ樹脂(“jER(登録商標)”1007、エポキシ当量:1925、三菱化学(株)製)
・ビスフェノールF型エポキシ樹脂(“jER(登録商標)”4007P、エポキシ当量:2270、三菱化学(株)製)
・ビスフェノールF型エポキシ樹脂(“jER(登録商標)”4010P、エポキシ当量:4400、三菱化学(株)製)
<エポキシ樹脂([B1]または[B2])>
・テトラグリシジルジアミノジフェニルメタン(“スミエポキシ(登録商標)”ELM434、住友化学(株)製、エポキシ当量:125)
・トリグリシジル-p-アミノフェノール(“jER(登録商標)”jER630、エポキシ当量:98、三菱化学(株)製))
・トリグリシジル-p-アミノフェノール(“アラルダイド(登録商標)”MY0500、エポキシ当量:110、ハイツマン・アドバンスドマテリアル(株)製)
・3,3’-テトラグリシジルジアミノジフェニルエーテル(TG3DDE、エポキシ当量:122、東レファインケミカル(株)製)
<エポキシ樹脂([B1])>
・3,3’-テトラグリシジルジアミノジフェニルスルホン(TG3DAS、エポキシ当量:136、小西化学工業(株)製)
<エポキシ樹脂([C1]または[C2])>
・ビスフェノールF型エポキシ樹脂(“エピクロン(登録商標)”830、エポキシ当量:170、DIC(株)製)
<エポキシ樹脂([C1])>
・フェノールノボラック樹脂“jER(登録商標)”152(三菱化学(株)製)
<硬化剤([D])>
・ジシアンジアミド(硬化剤、DICY7、三菱化学(株)製)。 <Epoxy resin ([A1] or [A2])>
-Bisphenol A type epoxy resin ("jER (registered trademark)" 1007, epoxy equivalent: 1925, manufactured by Mitsubishi Chemical Corporation)
-Bisphenol F type epoxy resin ("jER (registered trademark)" 4007P, epoxy equivalent: 2270, manufactured by Mitsubishi Chemical Corporation)
-Bisphenol F type epoxy resin ("jER (registered trademark)" 4010P, epoxy equivalent: 4400, manufactured by Mitsubishi Chemical Corporation)
<Epoxy resin ([B1] or [B2])>
Tetraglycidyl diaminodiphenyl methane (“Sumiepoxy (registered trademark)” ELM434, manufactured by Sumitomo Chemical Co., Ltd., epoxy equivalent: 125)
Triglycidyl-p-aminophenol ("jER (registered trademark)" jER630, epoxy equivalent: 98, manufactured by Mitsubishi Chemical Corporation)
Triglycidyl-p-aminophenol ("Araldide (registered trademark)" MY0500, epoxy equivalent: 110, manufactured by Heitzmann Advanced Material Co., Ltd.)
・ 3,3′-tetraglycidyldiaminodiphenyl ether (TG3DDE, epoxy equivalent: 122, manufactured by Toray Fine Chemical Co., Ltd.)
<Epoxy resin ([B1])>
・ 3,3′-tetraglycidyldiaminodiphenylsulfone (TG3DAS, epoxy equivalent: 136, manufactured by Konishi Chemical Co., Ltd.)
<Epoxy resin ([C1] or [C2])>
・ Bisphenol F type epoxy resin ("Epiclon (registered trademark)" 830, epoxy equivalent: 170, manufactured by DIC Corporation)
<Epoxy resin ([C1])>
・ Phenol novolac resin “jER (registered trademark)” 152 (manufactured by Mitsubishi Chemical Corporation)
<Curing agent ([D])>
Dicyandiamide (curing agent, DICY7, manufactured by Mitsubishi Chemical Corporation).
・S-B-M共重合体(“Nanostrength(登録商標)”E40:Sがポリスチレン(Tg:約90℃)、Bがポリ1,4-ブタジエン(Tg:約-90℃)、Mがポリメタクリル酸メチル(Tg:約130℃)からなるブロック共重合体、アルケマ(株)製)
・M-B-M共重合体(“Nanostrength(登録商標)”M22N:Bがポリブチルアクリレート(Tg:約-50℃)、Mがメタクリル酸メチルおよびメタクリル酸メチルよりもSP値の高い極性官能基含有モノマーの共重合体(Tg:約130℃)からなるブロック共重合体、アルケマ(株)製)。 <Block copolymer [E]>
SBM copolymer (“Nanostrength®” E40: S is polystyrene (Tg: about 90 ° C.), B is poly 1,4-butadiene (Tg: about −90 ° C.), M is poly Block copolymer consisting of methyl methacrylate (Tg: about 130 ° C., manufactured by Arkema Co., Ltd.)
MBM copolymer ("Nanostrength (registered trademark)" M22N: B is polybutyl acrylate (Tg: about -50 ° C), M is polar methacrylate having higher SP value than methyl methacrylate and methyl methacrylate A block copolymer comprising a copolymer of group-containing monomers (Tg: about 130 ° C., manufactured by Arkema Co., Ltd.).
・多官能エポキシ樹脂(“jER(登録商標)”1031S、エポキシ当量:200、三菱化学(株)製)
・ビスフェノールA型エポキシ樹脂(“jER(登録商標)”1001、エポキシ当量:470、三菱化学(株)製)
・ビスフェノールF型エポキシ樹脂(“jER(登録商標)”4004P、エポキシ当量:880、三菱化学(株)製)
・グリシジルフタルイミド(“デナコール(登録商標)”EX731、エポキシ当量:216、ナガセケムテックス(株)製)
・ポリエチレングリコール型エポキシ樹脂(“デナコール(登録商標)”EX821、エポキシ当量:185、ナガセケムテックス(株)製)
・N,N’-ジグリシジルアニリン(GAN、エポキシ当量:125、日本化薬(株))
・“ビニレック(登録商標)”PVF-K(ポリビニルホルマール)、JNC(株)製)
・DCMU99(3-(3,4-ジクロロフェニル)-1,1-ジメチルウレア、硬化促進剤、保土ヶ谷化学工業(株)製)。 <Other ingredients>
・ Polyfunctional epoxy resin ("jER (registered trademark)" 1031S, epoxy equivalent: 200, manufactured by Mitsubishi Chemical Corporation)
-Bisphenol A type epoxy resin ("jER (registered trademark)" 1001, epoxy equivalent: 470, manufactured by Mitsubishi Chemical Corporation)
-Bisphenol F type epoxy resin ("jER (registered trademark)" 4004P, epoxy equivalent: 880, manufactured by Mitsubishi Chemical Corporation)
・ Glycidylphthalimide ("Denacol (registered trademark)" EX731, epoxy equivalent: 216, manufactured by Nagase ChemteX Corporation)
Polyethylene glycol type epoxy resin (“Denacol (registered trademark)” EX821, epoxy equivalent: 185, manufactured by Nagase ChemteX Corporation)
・ N, N'-Diglycidylaniline (GAN, epoxy equivalent: 125, Nippon Kayaku Co., Ltd.)
・ "Vinylec (registered trademark)" PVF-K (polyvinyl formal), manufactured by JNC Corporation)
DCMU99 (3- (3,4-dichlorophenyl) -1,1-dimethylurea, curing accelerator, manufactured by Hodogaya Chemical Co., Ltd.)
測定装置としては、“HLC(登録商標)”8220GPC(東ソー株式会社製)、検出器としてUV-8000(254nm)、カラムにはTSK-G4000H(東ソー株式会社製)を用いた。測定するエポキシ樹脂をTHFに、濃度0.1mg/mlで溶解させ、これを流速1.0ml/分、温度40℃で測定した。測定サンプルの保持時間を、ポリスチレンの校正用サンプルの保持時間を用いて、分子量に換算して数平均分子量を求めた。 (2) Number average molecular weight measurement “HLC (registered trademark)” 8220GPC (manufactured by Tosoh Corporation) as a measuring device, UV-8000 (254 nm) as a detector, and TSK-G4000H (manufactured by Tosoh Corporation) as a column. Using. The epoxy resin to be measured was dissolved in THF at a concentration of 0.1 mg / ml, and this was measured at a flow rate of 1.0 ml / min and a temperature of 40 ° C. The retention time of the measurement sample was converted to molecular weight using the retention time of the polystyrene calibration sample, and the number average molecular weight was determined.
エポキシ樹脂組成物を真空中で脱泡した後、2mm厚のテフロン(登録商標)製スペーサーにより厚み2mmになるように設定したモールド中で、特に断らない限り130℃の温度で90分間硬化させ、厚さ2mmの板状の樹脂硬化物を得た。この樹脂硬化物から、幅10mm、長さ60mmの試験片を切り出し、インストロン万能試験機(インストロン社製)を用い、スパンを32mm、クロスヘッドスピードを100mm/分とし、JIS K7171(1994)に従って3点曲げを実施し、弾性率を測定した。サンプル数n=5で測定した値の平均値を弾性率の値とした。 (3) Elastic Modulus of Resin Cured Product After defoaming the epoxy resin composition in vacuum, 130% unless otherwise specified in a mold set to 2 mm thickness with a 2 mm thick Teflon (registered trademark) spacer. Curing was performed at a temperature of 90 ° C. for 90 minutes to obtain a plate-shaped resin cured product having a thickness of 2 mm. From this cured resin, a test piece having a width of 10 mm and a length of 60 mm was cut out, an Instron universal testing machine (manufactured by Instron) was used, the span was set to 32 mm, the crosshead speed was set to 100 mm / min, and JIS K7171 (1994). According to the above, three-point bending was performed and the elastic modulus was measured. The average value of the values measured with the number of samples n = 5 was taken as the elastic modulus value.
エポキシ樹脂組成物を真空中で脱泡した後、6mm厚のテフロン(登録商標)製スペーサーにより厚み6mmになるように設定したモールド中で、特に断らない限り130℃の温度で90分間硬化させ、厚さ6mmの板状の樹脂硬化物を得た。この樹脂硬化物から、幅12.7mm、長さ150mmの試験片を切り出し、ASTM D5045(1999)に従って、試験片を加工し、インストロン万能試験機(インストロン社製)を用い、測定をおこなった。試験片への初期の予亀裂の導入は、液体窒素温度まで冷やした剃刀の刃を試験片にあてハンマーで剃刀に衝撃を加えることで行った。ここでいう、樹脂靱性値とは、変形モードI(開口型)の臨界応力強度のことを指している。サンプル数n=5で測定した値の平均値を、樹脂靱性値とした。 (4) Measurement of resin toughness value of cured resin product After defoaming the epoxy resin composition in vacuum, it was particularly refused in a mold set to 6 mm thickness with a 6 mm thick Teflon (registered trademark) spacer. Unless otherwise specified, it was cured at a temperature of 130 ° C. for 90 minutes to obtain a plate-shaped resin cured product having a thickness of 6 mm. A test piece having a width of 12.7 mm and a length of 150 mm was cut out from the cured resin, processed according to ASTM D5045 (1999), and measured using an Instron universal tester (Instron). It was. The initial precrack was introduced into the test piece by applying a razor blade cooled to liquid nitrogen temperature to the test piece and applying an impact to the razor with a hammer. Here, the resin toughness value refers to the critical stress strength of deformation mode I (opening type). The average value of the values measured with the number of samples n = 5 was defined as the resin toughness value.
上記(4)で得られた樹脂硬化物を染色後、薄切片化し、透過型電子顕微鏡(TEM)を用いて下記の条件で透過電子像を取得した。染色剤は、モルホロジーに充分なコントラストが付くよう、OsO4とRuO4を樹脂組成に応じて使い分けた。
装置:H-7100透過型電子顕微鏡(日立(株)製)
加速電圧:100kV
倍率:10,000倍
透過電子像より、[A1]または[A2]リッチ相、[B1]または[B2]リッチ相および[E]リッチ相の構造周期を観察した。各成分の種類や比率により、樹脂硬化物の相分離構造は、両相連続構造や海島構造を形成するのでそれぞれについて以下のように測定した。 (5) Measurement of structural period After the resin cured product obtained in (4) was dyed, it was cut into thin sections and a transmission electron image was obtained under the following conditions using a transmission electron microscope (TEM). As the staining agent, OsO 4 and RuO 4 were properly used according to the resin composition so that the morphology was sufficiently contrasted.
Apparatus: H-7100 transmission electron microscope (manufactured by Hitachi, Ltd.)
Acceleration voltage: 100 kV
Magnification: 10,000 times The structure period of [A1] or [A2] rich phase, [B1] or [B2] rich phase, and [E] rich phase was observed from the transmission electron image. Depending on the type and ratio of each component, the phase separation structure of the resin cured product forms a biphasic continuous structure or a sea-island structure, and thus was measured as follows.
エポキシ樹脂組成物を、リバースロールコーターを使用し離型紙上に塗布し、樹脂フィルムを作製した。次に、該樹脂フィルム2枚をシート状に一方向に整列させた炭素繊維“トレカ(登録商標)”T800SC-24K(東レ(株)製、引張弾性率:294GPa、引張強度:5880MPa)の両面から重ね、加熱加圧してエポキシ樹脂組成物を炭素繊維に含浸させ、単位面積辺りの炭素繊維質量125g/m2、繊維質量含有率75質量%の、T800SC使い一方向プリプレグを作製した。また、炭素繊維としてT700SC-24K(東レ(株)製、引張弾性率:230GPa、引張強度:4900MPa)を用いたこと以外は上記と同様にして、単位面積辺りの炭素繊維質量125g/m2、繊維質量含有率75質量%の、T700SC使い一方向プリプレグも作製した。 (6) Preparation of prepreg The epoxy resin composition was applied onto release paper using a reverse roll coater to prepare a resin film. Next, both surfaces of carbon resin “TORAYCA (registered trademark)” T800SC-24K (manufactured by Toray Industries, Inc., tensile elastic modulus: 294 GPa, tensile strength: 5880 MPa) in which the two resin films are aligned in one direction in a sheet shape. The carbon fiber was impregnated with heat and pressure to impregnate the carbon fiber, and a T800SC unidirectional prepreg having a carbon fiber mass of 125 g / m 2 per unit area and a fiber mass content of 75 mass% was produced. Further, in the same manner as described above except that T700SC-24K (manufactured by Toray Industries, Inc., tensile elastic modulus: 230 GPa, tensile strength: 4900 MPa) was used as the carbon fiber, the mass of carbon fiber per unit area was 125 g / m 2 , A unidirectional prepreg using T700SC having a fiber mass content of 75% by mass was also produced.
上記(6)で作成した一方向プリプレグを、繊維方向を揃えて20ply積層した。次に、積層したプリプレグをナイロンフィルムで隙間のないように覆った。これをオートクレーブ中で135℃、内圧588kPaで2時間加熱加圧して硬化し、一方向積層板を作製した。 (7) Production of Unidirectional Laminate Plate The unidirectional prepreg produced in (6) above was laminated in 20 ply with the fiber direction aligned. Next, the laminated prepreg was covered with a nylon film so that there was no gap. This was cured by heating and pressing at 135 ° C. and an internal pressure of 588 kPa for 2 hours in an autoclave to produce a unidirectional laminate.
次の(a)~(e)の操作により、T800SC使い一方向プリプレグを、繊維方向が円筒軸方向に対して45°および-45°になるよう、各3plyを交互に積層し、さらにT800SC使い一方向プリプレグを、繊維方向が円筒軸方向に対して平行になるよう、3plyを積層し、内径が6.3mmの繊維強化複合材料製管状体を作製した。マンドレルとしては、直径6.3mm、長さ1000mmのステンレス製丸棒を使用した。 (8) Fabrication of cylindrical body made of fiber reinforced composite material for cylindrical Charpy impact test By the following operations (a) to (e), a unidirectional prepreg using T800SC was obtained with a fiber direction of 45 ° with respect to the cylindrical axis direction. 3ply is laminated alternately so that the angle is 45 °, and one-way prepreg using T800SC is laminated, 3ply is laminated so that the fiber direction is parallel to the cylindrical axis direction, and the inner diameter is 6.3 mm. A tubular material was made. As the mandrel, a stainless steel round bar having a diameter of 6.3 mm and a length of 1000 mm was used.
また、一方向プリプレグとして上記(6)で作成したT700SC使い一方向プリプレグを用いたこと以外は、上記(a)~(e)の操作を同様にしてT700SC使い繊維強化複合材料製管状体も作製した。 (E) Thereafter, the mandrel was extracted, and the wrapping tape was removed to obtain a fiber-reinforced composite material tubular body.
In addition, except that the unidirectional prepreg using T700SC prepared in (6) above was used as the unidirectional prepreg, a tubular body made of fiber reinforced composite material using T700SC was prepared in the same manner as the above operations (a) to (e). did.
上記(8)で得た繊維強化複合材料製管状体を長さ60mmでカットし、内径6.3mm、長さ60mmの試験片を作製した。秤量300kg・cmで管状体の側面から衝撃を与えてシャルピー衝撃試験を行った。振り上がり角から、下記の式、
E=WR[(cosβ-cosα)-(cosα'-cosα)(α+β)/(α+α')]
E:吸収エネルギー(J)
WR:ハンマーの回転軸の周りのモーメント(N・m)
α:ハンマーの持ち上げ角度(°)
α’:ハンマーの持ち上げ角αから空振りさせたときの振り上がり角(°)
β:試験片破断後のハンマーの振り上がり角(°)
に従って衝撃の吸収エネルギーを計算した。なお、試験片にはノッチ(切り欠き)は導入していない。測定数はn=5で行い、平均値をシャルピー衝撃値とした。 (9) Charpy impact test of fiber reinforced composite material tubular body The fiber reinforced composite material tubular body obtained in (8) above was cut to a length of 60 mm to produce a test piece having an inner diameter of 6.3 mm and a length of 60 mm. . A Charpy impact test was performed by applying an impact from the side of the tubular body at a weight of 300 kg · cm. From the swing angle, the following formula:
E = WR [(cosβ−cosα) − (cosα′−cosα) (α + β) / (α + α ′)]
E: Absorbed energy (J)
WR: Moment around the rotation axis of the hammer (N · m)
α: Hammer lift angle (°)
α ': Swing angle when the hammer is swung from the lift angle α (°)
β: Hammer swing angle after test specimen breakage (°)
The absorbed energy of impact was calculated according to Note that notches (notches) are not introduced into the test piece. The number of measurements was n = 5, and the average value was the Charpy impact value.
繊維強化複合材料の曲げ強度の指標として、一方向積層板の0°曲げ強度を測定した。一方向積層板を、厚み2mm、幅15mm、長さ100mmとなるように試験片を切り出した。インストロン万能試験機(インストロン社製)を用い、クロスヘッド速度5.0mm/分、スパン80mm、圧子径10mm、支点径4mmで試験片の測定を行ない、曲げ強度を計算した。また、作製したプリプレグの目付に基づいて、実Vfを求めた後、得られた曲げ強度をVf60%に換算した。 (10) Method for Measuring 0 ° Bending Strength of Unidirectional Laminate The 0 ° bending strength of the unidirectional laminated plate was measured as an index of bending strength of the fiber reinforced composite material. A test piece was cut out of the unidirectional laminate so as to have a thickness of 2 mm, a width of 15 mm, and a length of 100 mm. Using an Instron universal testing machine (Instron), the test piece was measured at a crosshead speed of 5.0 mm / min, a span of 80 mm, an indenter diameter of 10 mm, and a fulcrum diameter of 4 mm, and the bending strength was calculated. Moreover, after calculating | requiring real Vf based on the fabric weight of the produced prepreg, the obtained bending strength was converted into Vf60%.
環球法JIS-K7234(2008年)にて測定した。 (11) Softening point measurement (ring and ball method)
Measured by ring and ball method JIS-K7234 (2008).
上記(3)と同様の方法で作製した樹脂硬化物をダイヤモンドカッターで幅13mm、長さ35mmに切り出し、試験片とした。試験片を動的粘弾性測定装置(DMAQ800:ティー・エイ・インスツルメンツ社製)を用い、40℃~250℃まで昇温速度5℃/分で昇温し、周波数1.0Hzの曲げモードでガラス転移温度の測定を行った。このときの貯蔵弾性率のオンセット温度をガラス転移温度とした。表2~5にその結果を示す。ただし、相分離構造を有する樹脂硬化物のガラス転移温度測定では、樹脂硬化物のガラス転移温度が2つ生じる場合があり、表2~5に記載のガラス転移温度は、低い方のガラス転移温度である。 (12) Measurement of glass transition temperature of epoxy component of cured resin product A cured resin product produced by the same method as in (3) above was cut out to a width of 13 mm and a length of 35 mm with a diamond cutter to obtain a test piece. Using a dynamic viscoelasticity measuring device (DMAQ800: manufactured by TA Instruments Inc.), the test piece was heated from 40 ° C. to 250 ° C. at a heating rate of 5 ° C./min, and the glass was bent in a frequency mode of 1.0 Hz. The transition temperature was measured. The onset temperature of the storage elastic modulus at this time was defined as the glass transition temperature. Tables 2 to 5 show the results. However, in the measurement of the glass transition temperature of the cured resin having a phase separation structure, two glass transition temperatures of the cured resin may occur, and the glass transition temperatures shown in Tables 2 to 5 are the lower glass transition temperatures. It is.
エポキシ樹脂[A1]または[A2]としてjER1007を40部、エポキシ樹脂[B1]または[B2]としてjER630を20部、エポキシ樹脂[C1]または[C2]としてエピクロン830を40部、硬化剤[D]としてDICY7を全エポキシ樹脂成分のエポキシ基に対し、活性水素基が0.9当量となる量、および硬化促進剤としてDCMU99を2部用いて、エポキシ樹脂組成物を調製した。得られた樹脂組成物の80℃での粘度は良好であった。得られたエポキシ樹脂組成物を2.5℃/分で昇温し、130℃で90分間かけて硬化した。得られた樹脂硬化物は、微細な相分離構造を形成し、力学特性は良好であった。得られたエポキシ樹脂組成物と炭素繊維としてT800SC-24Kを用いて、前記のようにしてプリプレグを作成した。得られたプリプレグを用いて、前記のようにして作製した繊維強化複合材料製管状体の耐衝撃特性および一方向積層板の0°曲げ強度は、良好であった。結果を表2に示す。 Example 1
40 parts of jER1007 as epoxy resin [A1] or [A2], 20 parts of jER630 as epoxy resin [B1] or [B2], 40 parts of Epicron 830 as epoxy resin [C1] or [C2], curing agent [D ] An epoxy resin composition was prepared using DICY7 as an amount of 0.9 equivalent of active hydrogen groups with respect to the epoxy groups of all epoxy resin components and 2 parts of DCMU99 as a curing accelerator. The resulting resin composition had a good viscosity at 80 ° C. The resulting epoxy resin composition was heated at 2.5 ° C./min and cured at 130 ° C. for 90 minutes. The obtained cured resin formed a fine phase separation structure and had good mechanical properties. Using the obtained epoxy resin composition and T800SC-24K as carbon fiber, a prepreg was prepared as described above. Using the obtained prepreg, the impact resistance of the fiber-reinforced composite material tubular body produced as described above and the 0 ° bending strength of the unidirectional laminate were good. The results are shown in Table 2.
表2~5に示す組成に変更した以外は、実施例1と同様に、エポキシ樹脂組成物を調製した。評価結果を表2~5に示す。各実施例のエポキシ樹脂組成物から得られた樹脂硬化物は、いずれも微細な相分離構造を形成し、力学特性は良好であった。また、得られたエポキシ樹脂組成物と炭素繊維からなるプリプレグを用いて作製した繊維強化複合材料製管状体の耐衝撃特性および一方向積層板の0°曲げ強度は、良好であった。 (Examples 2 to 26, Comparative Examples 1 to 11)
Epoxy resin compositions were prepared in the same manner as in Example 1 except that the compositions shown in Tables 2 to 5 were changed. The evaluation results are shown in Tables 2-5. The cured resin obtained from the epoxy resin composition of each example formed a fine phase separation structure and had good mechanical properties. Moreover, the impact resistance property and the 0 ° bending strength of the unidirectional laminate were good for the tubular body made of fiber-reinforced composite material produced using the prepreg composed of the epoxy resin composition and carbon fiber obtained.
比較例10のエポキシ樹脂組成物は、エポキシ樹脂[A1]または[A2]を用いていないために、得られた樹脂硬化物は、均一構造を形成し、樹脂靱性値が著しく不足した。その結果、得られたエポキシ樹脂と炭素繊維を用いて作製した繊維強化複合材料製管状体の耐衝撃特性が不足した。 Since the epoxy resin composition of Comparative Example 9 did not use the epoxy resin [C1] or [C2], the obtained cured resin formed a coarse phase separation structure and the resin toughness value was remarkably insufficient. As a result, the impact resistance of the fiber-reinforced composite material tubular body produced using the resulting epoxy resin and carbon fiber was insufficient.
Since the epoxy resin composition of Comparative Example 10 did not use the epoxy resin [A1] or [A2], the obtained cured resin formed a uniform structure, and the resin toughness value was extremely insufficient. As a result, the impact resistance of the fiber-reinforced composite material tubular body produced using the resulting epoxy resin and carbon fiber was insufficient.
Claims (13)
- エポキシ樹脂[A1]、エポキシ樹脂[B1]、エポキシ樹脂[C1]および硬化剤[D]を含むエポキシ樹脂組成物であって、[A1]は軟化点が90℃以上のビスフェノール型エポキシ樹脂、[B1]は3官能以上のアミン型エポキシ樹脂、そして[C1]数平均分子量450以下のビスフェノールF型エポキシ樹脂であり、かつ、エポキシ樹脂[A1]~[C1]が全エポキシ樹脂成分100質量部に対して、[A1]20~50質量部、[B1]30~50質量部および[C1]10~40質量部の配合比を満たす、エポキシ樹脂組成物。 An epoxy resin composition comprising an epoxy resin [A1], an epoxy resin [B1], an epoxy resin [C1] and a curing agent [D], wherein [A1] is a bisphenol type epoxy resin having a softening point of 90 ° C. or higher, [ B1] is a tri- or higher functional amine type epoxy resin, and [C1] a bisphenol F type epoxy resin having a number average molecular weight of 450 or less, and the epoxy resins [A1] to [C1] are contained in 100 parts by mass of all epoxy resin components. On the other hand, an epoxy resin composition satisfying a compounding ratio of [A1] 20 to 50 parts by mass, [B1] 30 to 50 parts by mass and [C1] 10 to 40 parts by mass.
- エポキシ樹脂組成物を硬化させて得られる樹脂硬化物が、[A1]リッチ相と[B1]リッチ相を有してなる相分離構造を有し、その相分離構造周期が1nm~5μmである、請求項1に記載のエポキシ樹脂組成物。 The cured resin obtained by curing the epoxy resin composition has a phase separation structure having [A1] rich phase and [B1] rich phase, and the phase separation structure period is 1 nm to 5 μm. The epoxy resin composition according to claim 1.
- エポキシ樹脂[A2]、エポキシ樹脂[B2]、エポキシ樹脂[C2]および硬化剤[D]を含み、かつ、以下の条件(1)~(4)を満たすエポキシ樹脂組成物:
(1)エポキシ樹脂[B2]を硬化剤[D]と反応し硬化させて得られる樹脂硬化物[B2’]のSP値が、エポキシ樹脂[A2]および[C2]をそれぞれ硬化剤[D]と反応し硬化させて得られる樹脂硬化物[A2’]および[C2’]のいずれのSP値に対してよりも1.2以上大きい;
(2)エポキシ樹脂[A2]の軟化点が90℃以上であり、かつエポキシ樹脂[B2]と[C2]の軟化点がいずれも50℃以下である;
(3)エポキシ樹脂[C2]と、エポキシ樹脂[C2]のエポキシ基に対し活性水素基が0.9当量のジシアンジアミドと、エポキシ樹脂[C2]100質量部に対して2質量部の3-(3,4-ジクロロフェニル)-1,1-ジメチルウレアからなるエポキシ樹脂組成物を、室温から130℃まで2.5℃/分で昇温し、130℃で90分間反応させて得られる樹脂硬化物の弾性率が、3.5GPa以上である;および
(4)エポキシ樹脂組成物を硬化させて得られる樹脂硬化物が、[A2]リッチ相と[B2]リッチ相を含む相分離構造を有し、その相分離構造周期が1nm~1μmである。 An epoxy resin composition containing an epoxy resin [A2], an epoxy resin [B2], an epoxy resin [C2] and a curing agent [D] and satisfying the following conditions (1) to (4):
(1) The SP value of the cured resin [B2 ′] obtained by reacting the epoxy resin [B2] with the curing agent [D] and curing the epoxy resin [A2] and [C2] is the curing agent [D]. Greater than the SP value of any of the cured resin products [A2 ′] and [C2 ′] obtained by reacting with and curing the resin;
(2) The softening point of the epoxy resin [A2] is 90 ° C. or higher, and the softening points of the epoxy resins [B2] and [C2] are both 50 ° C. or lower;
(3) Epoxy resin [C2], dicyandiamide having an active hydrogen group of 0.9 equivalent to the epoxy group of epoxy resin [C2], and 2 parts by mass of 3- (3) to 100 parts by mass of epoxy resin [C2] Cured resin obtained by heating an epoxy resin composition comprising 3,4-dichlorophenyl) -1,1-dimethylurea from room temperature to 130 ° C. at a rate of 2.5 ° C./min and reacting at 130 ° C. for 90 minutes. And (4) a cured resin obtained by curing the epoxy resin composition has a phase separation structure including [A2] rich phase and [B2] rich phase. The period of the phase separation structure is 1 nm to 1 μm. - [A2]は軟化点が90℃以上のビスフェノール型エポキシ樹脂、[B2]は3官能以上のアミン型エポキシ樹脂、そして[C2]数平均分子量450以下のビスフェノールF型エポキシ樹脂であり、かつ、エポキシ樹脂[A2]~[C2]が全エポキシ樹脂成分100質量部に対して、[A2]20~50質量部、[B2]30~50質量部および[C2]10~40質量部の配合比を満たす請求項3に記載のエポキシ樹脂組成物。 [A2] is a bisphenol type epoxy resin having a softening point of 90 ° C. or higher, [B2] is a trifunctional or higher amine type epoxy resin, and [C2] a bisphenol F type epoxy resin having a number average molecular weight of 450 or lower, and an epoxy Resins [A2] to [C2] have a mixing ratio of [A2] 20 to 50 parts by mass, [B2] 30 to 50 parts by mass and [C2] 10 to 40 parts by mass with respect to 100 parts by mass of all epoxy resin components. The epoxy resin composition according to claim 3, which is satisfied.
- エポキシ樹脂[B1]または[B2]が3官能のアミノフェノール型エポキシ樹脂である、請求項1~4のいずれかに記載のエポキシ樹脂組成物。 The epoxy resin composition according to any one of claims 1 to 4, wherein the epoxy resin [B1] or [B2] is a trifunctional aminophenol type epoxy resin.
- 硬化剤[D]がジシアンジアミドまたはその誘導体である、請求項1~5のいずれかに記載のエポキシ樹脂組成物。 The epoxy resin composition according to claim 1, wherein the curing agent [D] is dicyandiamide or a derivative thereof.
- さらに、S-B-M、B-MおよびM-B-Mからなる群から選ばれる少なくとも1種のブロック共重合体[E]を、全エポキシ樹脂成分100質量部に対して1~10質量部含む、請求項1~6に記載のエポキシ樹脂組成物;
ここで、前記のS、BおよびMで表される各ブロックは、共有結合によって直接、もしくは、何らかの化学構造を介して連結されており、ブロックMはポリメタクリル酸メチルのホモポリマーまたは、メタクリル酸メチルを50質量%以上含むコポリマーからなるブロックであり、ブロックBはブロックMに非相溶で、かつ、そのガラス転移温度が20℃以下であるブロックであり、ブロックSはブロックBおよびMに非相溶で、かつ、そのガラス転移温度が、ブロックBのガラス転移温度よりも高いブロックである。 Further, at least one block copolymer [E] selected from the group consisting of SBM, BM, and MBM is added in an amount of 1 to 10 masses per 100 mass parts of the total epoxy resin component. The epoxy resin composition according to claim 1 comprising 6 parts;
Here, each of the blocks represented by S, B and M is linked directly or via some chemical structure via a covalent bond, and the block M is a polymethyl methacrylate homopolymer or methacrylic acid. A block comprising a copolymer containing 50% by mass or more of methyl, block B is a block incompatible with block M and has a glass transition temperature of 20 ° C. or less, and block S is non-blocking to blocks B and M The block is compatible and has a glass transition temperature higher than that of the block B. - 前記ブロック共重合体[E]が、M-B-Mで表されるブロック共重合体であり、Mブロックがメタクリル酸メチルよりもSP値の高いモノマーを共重合成分として含有する、請求項7に記載のエポキシ樹脂組成物。 The block copolymer [E] is a block copolymer represented by MBM, and the M block contains a monomer having a higher SP value than methyl methacrylate as a copolymer component. The epoxy resin composition described in 1.
- 前記ブロック共重合体[E]におけるブロック共重合体のブロックBが、ポリ1,4-ブタジエンまたはポリ(ブチルアクリレート)である、請求項7に記載のエポキシ樹脂組成物。 The epoxy resin composition according to claim 7, wherein block B of the block copolymer in the block copolymer [E] is poly1,4-butadiene or poly (butyl acrylate).
- エポキシ樹脂組成物の80℃における粘度が0.5~200Pa・sであり、かつ、硬化させて得られる樹脂硬化物の樹脂靱性値が1.3MPa・m0.5以上である、請求項1~9のいずれかに記載のエポキシ樹脂組成物。 2. The epoxy resin composition has a viscosity at 80 ° C. of 0.5 to 200 Pa · s, and a cured resin obtained by curing has a resin toughness value of 1.3 MPa · m 0.5 or more. 10. The epoxy resin composition according to any one of 1 to 9.
- 請求項1~10のいずれかに記載のエポキシ樹脂組成物と強化繊維を含むプリプレグ。 A prepreg comprising the epoxy resin composition according to any one of claims 1 to 10 and a reinforcing fiber.
- 請求項11に記載のプリプレグを硬化させてなる繊維強化複合材料。 A fiber-reinforced composite material obtained by curing the prepreg according to claim 11.
- 請求項1~10のいずれかに記載のエポキシ樹脂組成物の硬化物と、強化繊維を含む繊維強化複合材料。 A fiber-reinforced composite material comprising a cured product of the epoxy resin composition according to any one of claims 1 to 10 and reinforcing fibers.
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Also Published As
Publication number | Publication date |
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KR20130108351A (en) | 2013-10-02 |
EP2623533A1 (en) | 2013-08-07 |
RU2013119741A (en) | 2014-11-10 |
TWI513755B (en) | 2015-12-21 |
CN103140536A (en) | 2013-06-05 |
KR101569595B1 (en) | 2015-11-16 |
US20130217805A1 (en) | 2013-08-22 |
EP2623533A4 (en) | 2017-10-18 |
US9738782B2 (en) | 2017-08-22 |
CA2811881A1 (en) | 2012-04-05 |
TW201224048A (en) | 2012-06-16 |
EP2623533B1 (en) | 2020-04-29 |
CN103140536B (en) | 2015-09-23 |
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